Liquid-crystalline compounds

ABSTRACT

The invention relates to liquid-crystalline compounds of the formula (I) in which R 1 , R 2 , A 1 , A 2 , A 3 , A 4 , Z 1 , Z 2 , Z 3 , a, b and c have the meanings indicated in Claim  1,  and to liquid-crystalline media comprising at least one compound of the (I) and to electro-optical displays containing a liquid-crystalline medium of this type.

The present invention relates to liquid-crystalline compounds and to a liquid-crystalline medium, to the use thereof for electro-optical purposes, and to displays containing this medium.

Liquid crystals are used principally as dielectrics in display devices, since the optical properties of such substances can be modified by an applied voltage. Electro-optical devices based on liquid crystals are extremely well known to the person skilled in the art and can be based on various effects. Examples of such devices are cells having dynamic scattering, DAP (deformation of aligned phases) cells, guest/host cells, TN cells having a twisted nematic structure, STN (supertwisted nematic) cells, SBE (super-birefringence effect) cells and OMI (optical mode interference) cells. The commonest display devices are based on the Schadt-Helfrich effect and have a twisted nematic structure.

The liquid-crystal materials must have good chemical and thermal stability and good stability to electric fields and electromagnetic radiation. Furthermore, the liquid-crystal materials should have low viscosity and produce short addressing times, low threshold voltages and high contrast in the cells.

They should furthermore have a suitable mesophase, for example a nematic or cholesteric mesophase for the above-mentioned cells, at the usual operating temperatures, i.e. in the broadest possible range above and below room temperature. Since liquid crystals are generally used as mixtures of a plurality of components, it is important that the components are readily miscible with one another. Further properties, such as the electrical conductivity, the dielectric anisotropy and the optical anisotropy, have to satisfy various requirements depending on the cell type and area of application. For example, materials for cells having a twisted nematic structure should have positive dielectric anisotropy and low electrical conductivity.

For example, for matrix liquid-crystal displays with integrated non-linear elements for switching individual pixels (MLC displays), media having large positive dielectric anisotropy, broad nematic phases, relatively low birefringence, very high specific resistance, good UV and temperature stability and low vapour pressure are desired.

Matrix liquid-crystal displays of this type are known. Non-linear elements which can be used for individual switching of the individual pixels are, for example, active elements (i.e. transistors). The term “active matrix” is then used, where a distinction can be made between two types:

-   1. MOS (metal oxide semiconductor) or other diodes on a silicon     wafer as substrate. -   2. Thin-film transistors (TFTs) on a glass plate as substrate.

The use of single-crystal silicon as substrate material restricts the display size, since even modular assembly of various part-displays results in problems at the joins.

In the case of the more promising type 2, which is preferred, the electro-optical effect used is usually the TN effect. A distinction is made between two technologies: TFTs comprising compound semiconductors, such as, for example, CdSe, or TFTs based on polycrystalline or amorphous silicon. Intensive work is being carried out world-wide on the latter technology.

The TFT matrix is applied to the inside of one glass plate of the display, while the other glass plate carries the transparent counterelectrode on its inside. Compared with the size of the pixel electrode, the TFT is very small and has virtually no adverse effect on the image. This technology can also be extended to fully colour-capable displays, in which a mosaic of red, green and blue filters is arranged in such a way that a filter element is opposite each switchable pixel.

The TFT displays usually operate as TN cells with crossed polarisers in transmission and are back-lit.

The term MLC displays here encompasses any matrix display with integrated non-linear elements, i.e., besides the active matrix, also displays with passive elements, such as varistors or diodes (MIM=metal-insulator-metal).

MLC displays of this type are particularly suitable for TV applications (for example pocket television sets) or for high-information displays for computer applications (laptops) and in automobile or aircraft construction. Besides problems regarding the angle dependence of the contrast and the response times, difficulties also arise in MLC displays due to insufficiently high specific resistance of the liquid-crystal mixtures [TOGASHI, S., SEKI-GUCHI, K., TANABE, H., YAMAMOTO, E., SORIMACHI, K., TAJIMA, E., WATANABE, H., SHIMIZU, H., Proc. Eurodisplay 84, September 1984: A 210-288 Matrix LCD Controlled by Double Stage Diode Rings, p.141 ff, Paris; STROMER, M., Proc. Eurodisplay 84, September 1984: Design of Thin Film Transistors for Matrix Addressing of Television Liquid Crystal Displays, p. 145 ff, Paris]. With decreasing resistance, the contrast of an MLC display deteriorates, and the problem of after-image elimination may occur. Since the specific resistance of the liquid-crystal mixture generally drops over the life of an MLC display owing to interaction with the interior surfaces of the display, a high (initial) resistance is very important in order to obtain acceptable service lives. In particular in the case of low-volt mixtures, it was hitherto impossible to achieve very high specific resistance values. It is furthermore important that the specific resistance exhibits the smallest possible increase with increasing temperature and after heating and/or UV exposure. The low-temperature properties of the mixtures from the prior art are also particularly disadvantageous. It is demanded that no crystallisation and/or smectic phases occur, even at low temperatures, and the temperature dependence of the viscosity is as low as possible. The MLC displays from the prior art thus do not meet today's requirements.

There thus continues to be a great demand for MLC displays having very high specific resistance at the same time as a large working-temperature range, short response times even at low temperatures and low threshold voltage which do not have these disadvantages, or only do so to a reduced extent.

In TN (Schadt-Helfrich) cells, media are desired which facilitate the following advantages in the cells:

-   -   extended nematic phase range (in particular down to low         temperatures)     -   the ability to switch at extremely low temperatures (outdoor         use, auto-mobile, avionics)     -   increased resistance to UV radiation (longer service life).

The media available from the prior art do not allow these advantages to be achieved while simultaneously retaining the other parameters.

In the case of supertwisted (STN) cells, media are desired which enable greater multiplexability and/or lower threshold voltages and/or broader nematic phase ranges (in particular at low temperatures). To this end, a further widening of the available parameter latitude (clearing point, smectic-nematic transition or melting point, viscosity, dielectric parameters, elastic parameters) is urgently desired.

The invention has the object of providing media, in particular for MLC, IPS, TN or STN displays of this type, which do not have the above-mentioned disadvantages or only do so to a reduced extent, and preferably simultaneously have very high specific resistance values and low threshold voltages. This object requires liquid-crystalline compounds which have a high clearing point and low rotational viscosity.

It has now been found that this object can be achieved if the liquid-crystal-line compounds according to the invention are used.

The invention thus relates to liquid-crystalline compounds of the formula I

in which

-   R¹ and R² each, independently of one another, denote H, halogen, a     halogenated or unsubstituted alkyl or alkoxy radical having 1 to 15     C atoms, where, in addition, one or more CH₂ groups in these     radicals may each, independently of one another, be replaced by     —C≡C—, —CH═CH—, —O—, —CO—O— or —O—CO— in such a way that O atoms are     not linked directly to one another, where one of the radicals R¹ and     R² may alternatively denote CN, OCN, SCN, NCS or SF₅, -   A¹, A₂, A₃     and A⁴ each, independently of one another, denote

-   Z¹, Z² and Z³ each, independently of one another, denote —CO—O—,     —O—CO—, —CF₂O—, —OCF₂—, —CH₂O—, —OCH₂—, —CH₂CH₂—, —(CH₂)₄—, —C₂F₄—,     —CH₂CF₂—, —CF₂CH₂—, —CF═CF—, —CH═CH—, —C≡C— or a single bond, and -   a, b and c each, independently of one another, denote 0, 1, 2 or 3,     where a+b+c≦3.

The invention furthermore relates to the use of the compounds of the formula I in liquid-crystalline media.

The compounds of the formula I have a broad range of applications. Depending on the choice of substituents, these compounds can serve as base materials of which liquid-crystalline media are predominantly composed; however, it is also possible to add compounds of the formula I to liquid-crystalline base materials from other classes of compound in order, for example, to modify the dielectric and/or optical anisotropy of a dielectric of this type and/or in order to optimise its threshold voltage and/or its viscosity.

In the pure state, the compounds of the formula I are colourless and form liquid-crystalline mesophases in a temperature range which is favourably located for electro-optical use. In particular, the compounds according to the invention are distinguished by their broad nematic phase range. In liquid-crystalline mixtures, the substances according to the invention suppress the smectic phases and result in a significant improvement in the low-temperature storage stability. They are stable chemically, thermally and to light.

The invention relates, in particular, to the compounds of the formula I in which R¹ is alkyl or alkenyl, and R² is halogen or OCF₃. Halogen is preferably F, furthermore Cl.

Particular preference is given to compounds of the formula I in which a=0, furthermore a=1. Z¹, Z² and/or Z³ preferably denotes a single bond, furthermore —CF₂O—, —OCF₂—, —C₂F₄—, —CH₂O—, —OCH₂— or —COO—.

A¹, A², A³ and A⁴ preferably denote

A⁴ denotes in particular

Particular preference is given to compounds of the formulae IA

in which

a and b each denote 0, 1 or 2 and a+b=1 or 2. Preferably, a=1 and b=0 or a=0 and b=1. Preferably, L¹=F and L²=H or fluorine, in particular L¹=L²=fluorine.

R¹ preferably denotes alkyl, alkoxy, alkenyl or alkenyloxy. R² preferably denotes F, Cl, OCF₃, OCHF₂, OCHFCF₃, OCF₂CHFCF₃, CN, SF₅, NCS or SCN, in particular F or OCF₃, and R¹ preferably denotes straight-chain alkyl or alkenyl. L¹ and L² each, independently of one another, denote H or F. Particular preference is given to compounds in which X=L¹=L²=fluorine, furthermore X═OCF₃ and. L¹=L²=F.

Particularly preferred compounds of the formula I are the compounds of the formulae I1 to I31,

in which R¹ has the meaning indicated above. X has the meaning of R².

The compounds of the formula I can be separated into the enantiomers very easily by passing the racemate, for example, through a chiral HPLC column. The invention therefore relates to the compounds of the formula I both in the form of the racemate and the enantiomer.

The compounds of the formula I are prepared by methods known per se, as described in the literature (for example in the standard works, such as Houben-Weyl, Methoden der organischen Chemie [Methods of Organic Chemistry], Georg-Thieme-Verlag, Stuttgart), to be precise under reaction conditions which are known and suitable for the said reactions. Use can also be made here of variants which are known per se, but are not mentioned here in greater detail.

The compounds of the formula I can be prepared, for example, as follows:

The invention also relates to electro-optical displays (in particular STN or MLC displays having two plane-parallel outer plates, which, together with a frame, form a cell, integrated non-linear elements for switching individual pixels on the outer plates, and a nematic liquid-crystal mixture of positive dielectric anisotropy and high specific resistance which is located in the cell) which contain media of this type, and to the use of these media for electro-optical purposes.

The liquid-crystal mixtures according to the invention enable a significant widening of the available parameter latitude.

The achievable combinations of clearing point, viscosity at low temperature, thermal and UV stability and dielectric anisotropy are far superior to previous materials from the prior art.

The requirement for a high clearing point, a nematic phase at low temperature and a high Δε has hitherto only been satisfied to an inadequate extent. Although liquid-crystal mixtures such as, for example, MS 99295 (Merck KGaA, Darmstadt, Germany) have comparable clearing points and low-temperature stabilities, they have, however, relatively high Δn values and also higher threshold voltages of about ≦1.7 V.

Other mixture systems have comparable viscosities and Δε values, but only have clearing points in the region of 60° C.

The liquid-crystal mixtures according to the invention, while retaining the nematic phase down to −20° C. and preferably down to −30° C., particularly preferably down to −40° C., enable clearing points above 80°, preferably above 90°, particularly preferably above 100° C., simultaneously dielectric anisotropy values Δε of ≧4, preferably ≧6, and a high value for the specific resistance to be achieved, enabling excellent STN and MLC displays to be obtained. In particular, the mixtures are characterised by low operating voltages. The TN thresholds are below 1.5 V, preferably below 1.3 V.

It goes without saying that, through a suitable choice of the components of the mixtures according to the invention, it is also possible for higher clearing points (for example above 110°) to be achieved at higher threshold voltage or lower clearing points to be achieved at lower threshold voltages with retention of the other advantageous properties. At viscosities correspondingly increased only slightly, it is likewise possible to obtain mixtures having greater Δε and thus lower thresholds. The MLC displays according to the invention preferably operate at the first Gooch and Tarry transmission minimum [C. H. Gooch and H. A. Tarry, Electron. Lett. 10, 2-4, 1974; C. H. Gooch and H. A. Tarry, Appl. Phys., Vol. 8, 1575-1584, 1975], where, besides particularly favourable electro-optical properties, such as, for example, high steepness of the characteristic line and low angle dependence of the contrast (German Patent 30 22 818), a lower dielectric anisotropy is sufficient at the same threshold voltage as in an analogous display at the second minimum. This enables significantly higher specific resistance values to be achieved using the mixtures according to the invention at the first minimum than in the case of mixtures comprising cyano compounds. Through a suitable choice of the individual components and their proportions by weight, the person skilled in the art is able to set the birefringence necessary for a pre-specified layer thickness of the MLC display using simple routine methods.

The flow viscosity ν₂₀ at 20° C. is preferably <60 mm²·s⁻¹, particularly preferably <50 mm²·s⁻¹. The nematic phase range is preferably at least 90°, in particular at least 100°. This range preferably extends at least from −30° to +80°. The rotational viscosity γ₁ at 20° C. is preferably <200 mPa.s, particularly preferably <180 mPa.s, in particular <160 mPa.s.

Measurements of the capacity holding ratio (HR) [S. Matsumoto et al., Liquid Crystals 5, 1320 (1989); K. Niwa et al., Proc. SID Conference, San Francisco, June 1984, p. 304 (1984); G. Weber et al., Liquid Crystals 5, 1381 (1989)] have shown that mixtures according to the invention comprising compounds of the formula I exhibit a significantly smaller decrease in the HR with increasing temperature than analogous mixtures comprising cyanophenylcyclohexanes of the formula

or esters of the formula

instead of the compounds of the formula I.

The UV stability of the mixtures according to the invention is also considerably better, i.e. they exhibit a significantly smaller decrease in the HR on exposure to UV.

The media according to the invention are preferably based on a plurality of (preferably two, three or more) compounds of the formula I, i.e. the proportion of these compounds is 5-95%, preferably 10-60% and particularly preferably in the range 15-40%.

The individual compounds of the formulae I to IX and their sub-formulae which can be used in the media according to the invention are either known or they can be prepared analogously to the known compounds.

Preferred embodiments are indicated below:

-   -   The medium preferably comprises one, two or three homologous         compounds of the formula I, where each homologue is present in         the mixture in a maximum amount of 10%.     -   Medium additionally comprises one or more compounds selected         from the group consisting of the general formulae II to IX:

in which the individual radicals have the following meanings:

-   R⁰ n-alkyl, oxaalkyl, fluoroalkyl, alkenyloxy or alkenyl, each     having up to 9 C atoms, -   X⁰ F, Cl, halogenated alkyl, halogenated alkenyl, halogenated     alkenyloxy or halogenated alkoxy having up to 7 C atoms, -   Z⁰ —CH═CH—, —C₂H₄—, —(CH₂)₄—, —C₂F₄—, —CH₂O—, —OCH₂—, —CF═CF—,     —CF₂O—, —OCF₂— or —COO—, -   Y¹, Y², -   Y³ and Y⁴ each, independently of one another, H or F, and -   r 0 or 1.

The compound of the formula IV is preferably

-   -   The medium preferably comprises one or more compounds of the         formulae

in which R⁰ and Y² have the meanings indicated above.

-   -   The medium preferably comprises one, two or three, furthermore         four, homologues of the compounds selected from the group         consisting of H1 to H19 (n=1-7):

-   -   The medium additionally comprises one or more compounds selected         from the group consisting of the general formulae X to XV:

in which R⁰, X⁰, Y¹, Y², Y³ and Y⁴ each, independently of one another, have one of the meanings indicated in Claim 8. X^(0 a)preferably denotes F, Cl, CF₃, OCF₃ or OCHF₂. R⁰ preferably denotes alkyl, oxaalkyl, fluoroalkyl, alkenyl or alkenyloxy.

-   -   The proportion of compounds of the formulae I to IX together in         the mixture as a whole is at least 50% by weight.     -   The proportion of compounds of the formula I in the mixture as a         whole is 5 to 50% by weight.     -   The proportion of compounds of the formula II in the mixture as         a whole is 3-40% by weight.     -   The proportion of compounds of the formulae II to IX in the         mixture as a whole is 30 to 70% by weight.

-   -   The medium comprises compounds of the formulae II, III, IV, V,         VI, VII, VIII and/or IX.     -   R⁰ is straight-chain alkyl or alkenyl having 2 to 7 C atoms.     -   The medium essentially consists of compounds of the formulae I         to XV.     -   The medium comprises 5-40% by weight of compounds of the         formulae H17 and/or H18.     -   The medium comprises further compounds, preferably selected from         the following group consisting of the general formulae XVI to         XX:

in which R⁰ and X⁰ have the meanings indicated above, and the 1,4-phenylene rings may be substituted by CN, chlorine or fluorine. The 1,4-phenylene rings are preferably mono- or polysubstituted by fluorine atoms.

-   -   The medium comprises further compounds, preferably selected from         the following group consisting of the formulae RI to RIX

in which

-   R⁰ denotes n-alkyl, oxaalkyl, fluoroalkyl, alkenyloxy or alkenyl,     each having up to 9 C atoms, -   d denotes 0, 1 or 2, -   Y¹ denotes H or F, -   alkyl or -   alkyl* each, independently of one another, denote a straight-chain     or branched alkyl radical having 1-9 C atoms, -   alkenyl or -   alkenyl* each, independently of one another, denote a straight-chain     or branched alkenyl radical having up to 9 C atoms.     -   The medium preferably comprises one or more compounds of the         formulae

in which n and m each denote an integer from 1 to 9.

-   -   The I: (II+III+IV+V+VI+VII+VII+IX) weight ratio is preferably         1:10 to 10:1.     -   The medium essentially consists of compounds selected from the         group consisting of the general formulae I to XV.

It has been found that even a relatively small proportion of compounds of the formula I mixed with conventional liquid-crystal materials, but in particular with one or more compounds of the formula II, III, IV, V, VI, VII, VIII or IX results in a considerable lowering of the threshold voltage and in low birefringence values, with broad nematic phases with low smectic-nematic transition temperatures being observed at the same time, improving the storage stability. The compounds of the formulae I to IX are colourless, stable and readily miscible with one another and with other liquid-crystal materials.

The term “alkyl” or “alkyl*” encompasses straight-chain and branched alkyl groups having 1-9 carbon atoms, in particular the straight-chain groups methyl, ethyl, propyl, butyl, pentyl, hexyl and heptyl. Groups having 2-5 carbon atoms are generally preferred.

The term “alkenyl” or “alkenyl*” encompasses straight-chain and branched alkenyl groups having up to 9 carbon atoms, in particular the straight-chain groups. Particularly preferred alkenyl groups are C₂-C₇-1E-alkenyl, C₄-C₇-3E-alkenyl, C₅-C₇-4-alkenyl, C₆-C₇-5-alkenyl and C₇-6-alkenyl, in particular C₂-C₇-1E-alkenyl, C₄-C₇-3E-alkenyl and C₅-C₇-4-alkenyl. Examples of preferred alkenyl groups are vinyl, 1E-propenyl, 1E-butenyl, 1E-pentenyl, 1E -hexenyl, 1E-heptenyl, 3-butenyl, 3E-pentenyl, 3E-hexenyl, 3E-heptenyl, 4-pentenyl, 4Z-hexenyl, 4E-hexenyl, 4Z-heptenyl, 5-hexenyl, 6-heptenyl and the like. Groups having up to 5 carbon atoms are generally preferred.

The term “fluoroalkyl” preferably encompasses straight-chain groups having a terminal fluorine, i.e. fluoromethyl, 2-fluoroethyl, 3-fluoropropyl, 4-fluorobutyl, 5-fluoropentyl, 6-fluorohexyl and 7-fluoroheptyl. However, other positions of the fluorine are not excluded.

The term “oxaalkyl” preferably encompasses straight-chain radicals of the formula C_(n)H_(2n+1)—O—(CH₂)_(m), in which n and m each, independently of one another, denote 1 to 6. Preferably, n=1 and m denotes 1 to 6.

Through a suitable choice of the meanings of R⁰ and X⁰, the addressing times, the threshold voltage, the steepness of the transmission characteristic lines, etc., can be modified in the desired manner. For example, 1E -alkenyl radicals, 3E-alkenyl radicals, 2E-alkenyloxy radicals and the like generally result in shorter addressing times, improved nematic tendencies and a higher ratio of the elastic constants k₃₃ (bend) and k₁₁ (splay) compared with alkyl or alkoxy radicals. 4-alkenyl radicals, 3-alkenyl radicals and the like generally give lower threshold voltages and smaller values of k₃₃/k₁₁ compared with alkyl and alkoxy radicals.

A —CH₂CH₂- group in Z¹ and/or Z² generally results in higher values of k₃₃/k₁₁ compared with a single covalent bond. Higher values of k₃₃/k₁₁ facilitate, for example, flatter transmission characteristic lines in TN cells with a 90° twist (in order to achieve grey shades) and steeper transmission characteristic lines in STN, SBE and OMI cells (greater multiplexability), and vice versa.

The optimum mixing ratio of the compounds of the formulae I and II+III+IV+V+VI+VII+VII+VIII+IX depends substantially on the desired properties, on the choice of the components of the formulae I, II, III, IV, V, VI, VII, VIII and/or IX, and on the choice of any other components that may be present. Suitable mixing ratios within the range given above can easily be determined from case to case.

The total amount of compounds of the formulae I to XV in the mixtures according to the invention is not crucial. The mixtures can therefore comprise one or more further components for the purposes of optimisation of various properties. However, the observed effect on the addressing times and the threshold voltage is generally greater, the higher the total concentration of compounds of the formulae I to XV.

In a particularly preferred embodiment, the media according to the invention comprise compounds of the formulae II to IX (preferably II and/or III) in which X⁰ denotes OCF₃, OCHF₂, F, OCH═CF₂, OCF═CF₂, OCF₂CHFCF₃ or OCF₂—CF₂H. A favourable synergistic effect with the compounds of the formula I results in particularly advantageous properties.

The construction of the MLC display according to the invention from polarisers, electrode base plates and surface-treated electrodes corresponds to the conventional construction for displays of this type. The term conventional construction is broadly drawn here and also encompasses all derivatives and modifications of the MLC display, in particular including matrix display elements based on poly-Si TFT or MIM.

A significant difference between the displays according to the invention and the hitherto conventional displays based on the twisted nematic cell consists, however, in the choice of the liquid-crystal parameters of the liquid-crystal layer.

The liquid-crystal mixtures which can be used in accordance with the invention are prepared in a manner conventional per se. In general, the desired amount of the components used in lesser amount is dissolved in the components making up the principal constituent, advantageously at elevated temperature. It is also possible to mix solutions of the components in an organic solvent, for example in acetone, chloroform or methanol, and to remove the solvent again, for example by distillation, after thorough mixing.

The dielectrics may also comprise further additives known to the person skilled in the art and described in the literature, such as, for example stabilisers and antioxidants. For example, 0-15% of pleochroic dyes or chiral dopants can be added.

C denotes a crystalline phase, S a smectic phase, S_(C) a smectic C phase, S_(B) a smectic B phase, N a nematic phase and I the isotropic phase.

V₁₀ denotes the voltage for 10% transmission (viewing angle perpendicular to the plate surface). t_(on) denotes the switch-on time and t_(off) the switch-off time at an operating voltage corresponding to 2 times the value of V₁₀. Δn denotes the optical anisotropy and n_(o) the refractive index. Δε denotes the dielectric anisotropy (Δε=ε_(∥)−ε_(⊥), where ε_(∥) denotes the dielectric constant parallel to the longitudinal molecular axes and ε_(⊥) the dielectric constant perpendicular thereto). The electro-optical data were measured in a TN cell at the 1st minimum (i.e. at a d·Δn value of 0.5 μm) at 20° C., unless expressly stated otherwise. The optical data were measured at 20° C., unless expressly stated otherwise.

In the present application and in the examples below, the structures of the liquid-crystal compounds are indicated by means of acronyms, the transformation into chemical formulae taking place in accordance with Tables A and B below. All radicals C_(n)H_(2n+1) and C_(m)H_(2m+1) are straight-chain alkyl radicals having n and m C atoms respectively; n and m are each, independently of one another, 1, 2, 3, 4, 5, 6, 7, 8, 9, 10, 11, 12, 13, 14 or 15. The coding in Table B is self-evident. In Table A, only the acronym for the parent structure is indicated. In individual cases, the acronym for the parent structure is followed, separated by a dash, by a code for the substituents R¹, R², L¹ and L²:

Code for R¹, R², L¹, L² R¹ R² L¹ L² nm C_(n)H_(2n+1) C_(m)H_(2m+1) H H nOm C_(n)H_(2n+1) OC_(m)H_(2m+1) H H nO.m OC_(n)H_(2n+1) C_(m)H_(2m+1) H H n C_(n)H_(2n+1) CN H H nN.F C_(n)H_(2n+1) CN H F nF C_(n)H_(2n+1) F H H nOF OC_(n)H_(2n+1) F H H nCl C_(n)H_(2n+1) Cl H H nF.F C_(n)H_(2n+1) F H F nF.F.F C_(n)H_(2n+1) F F F nCF₃ C_(n)H_(2n+1) CF₃ H H nOCF₃ C_(n)H_(2n+1) OCF₃ H H nOCF₃.F C_(n)H_(2n+1) OCF₃ H F nOCF₂ C_(n)H_(2n+1) OCHF₂ H H nS C_(n)H_(2n+1) NCS H H rVsN C_(r)H_(2r+1)—CH═CH—C_(s)H_(2s)— CN H H rEsN C_(r)H_(2r+1)—O—C₂H_(2s)— CN H H nAm C_(n)H_(2n+1) COOC_(m)H_(2m+1) H H nOCCF₂.F.F C_(n)H_(2n+1) OCH₂CF₂H F F

Preferred mixture components are given in Tables A and B.

TABLE A

PYP

PYRP

BCH

CBC

CCH

CCP

CPTP

CEPTP

ECCP

CECP

EPCH

PCH

PTP

BECH

EBCH

CPC

B

FET-nF

CGG

CGU

CUP

CCQU

PGU

CCPC

TABLE B

CBC-nmF

PCH-nOm

FET-nCl

CP-nOCF₃

CCH-nOm

BCH-n.Fm

Inm

CBC-nm

ECCP-nm

CCH-n1EM

T-nFm

CGU-n-F

CCP-nOCF₃.F

CGG-n-F

CCP-nOCF₂.F(.F)

CCP-nF.F.F

CCGU-n-F

CGU-n-OXF

CUZU-n-F

CGU-n-O1DT

CCZU-n-F

CC-n-V1

CC-n-V

CCP-nOCF₃

BCH-nF.F.F

CDU-n-F

CWCQU-n-F

CCOC-n-m

CGZU-n-F

CUZP-n-F

CGU-1V-F

CCG-V-F

CGZP-n-F

UZP-n-N

CCP-V-m

CGZP-n-OT

CUZP-n-OT

CCQU-n-F

CCQG-n-F

Dec-U-n-F

Nap-U-n-F

CQGZP-n-F

CCQP-n-S

CPUQU-n-F

CCEEU-n-F

CEECU-n-F

CCQU-V-F

CCQU-1V-F

PUQU-n-F

CGUQU-n-F

PGU-n-F

PQU-Br-F

PUQU-F-F

IS-9003

ACQU-n-F

APUQU-n-F

AUUQPU-n-F

AUUQGU-n-F

ACQP-n-OT

ACQG-n-OT

ACQG-n-F

ACQGU-n-F

ACQGP-n-F

ACQPG-n-OT

ACQPU-n-F

AGUQU-n-F

AUUQU-n-F

AUUQU-n-T

AUUQP-n-T

AUUQU-n-OT

PGP-n-m

Table C shows possible dopants which are generally added to the mixtures according to the invention in amounts of 0.1 to 10% by weight.

TABLE C

C 15

CB 15

CM 21

R/S-811

CM 44

CM 45

CM 47

CN

R/S-2011

R/S-4011

R/S-5011

Stabilisers which can be added, for example, to the mixtures according to the invention are mentioned below.

TABLE D

The following examples are intended to explain the invention without restricting it. Above and below, percentages are per cent by weight. All temperatures are given in degrees Celsius. m.p. denotes melting point, cl.p. clearing point. Furthermore, C=crystalline state, N=nematic phase, S=smectic phase and I=isotropic phase. The data between these symbols represent the transition temperatures. Δn denotes optical anisotropy (589 nm, 20° C.), Δε the dielectric anisotropy (1 kHz, 20° C.). The flow viscosity ν₂₀ (mm²/sec) was determined at 20° C. The rotational viscosity γ₁ (mPa·s) was likewise determined at 20° C.

“Conventional work-up” means that water is added if necessary, the mixture is extracted with dichloromethane, diethyl ether, methyl tert-butyl ether or toluene, the phases are separated, the organic phase is dried and evaporated, and the product is purified by distillation under reduced pressure or crystallisation and/or chromatography. The following abbreviations are used:

-   n-BuLi 1.6 molar solution of n-butyllithium in n-hexane -   DMAP 4-(dimethylamino)pyridine -   THF tetrahydrofuran -   DCC N,N′-dicyclohexylcarbodiimide -   LDA lithium dimethylamide -   RT room temperature

EXAMPLE 1

Step 1.1

B is prepared analogously to Lit. a) R. Baker, A. L. Boyes, C. J. Swain, J. Chem. Soc. Perkin Trans. 1, 1990, 1415-1421; b) H. Hagiwara, T. Okabe, H. Ono, V. P. Kamat, T. Hoshi, T. Suzuku, M. Ando, J. Chem. Soc. Perkin Trans. 1, 2002, 895-900.

Step 1.2

207 mmol of BuLi (15% in hexane) are added dropwise at −50° C. to a solution of 207 mmol of 1,4-dibromobenzene in 250 ml of diethyl ether. A solution of 170 mmol of B in 50 ml of diethyl ether is then added dropwise at the same temperature, and the mixture is stirred for a further 30 minutes, allowed to come to 0° C. and subjected to conventional aqueous work-up. The crude product (51 g) is dissolved in 400 ml of CH₂Cl₂, and 400 mmol of triethylsilane are added at −75° C. 400 mmol of boron trifluoride etherate are added dropwise, during which the temperature must not rise above −70° C. The mixture is then allowed to come to −10° C., is hydrolysed using sat. NaHCO₃ solution and subjected to conventional aqueous work-up. The crude product comprises the trans/cis isomers in a ratio of 9:1. The product is recrystallised from pentane at −20° C.

Step 1.3

73 mmol of C are dissolved in 200 ml of THF and cooled to −70° C. Firstly 73 mmol of BuLi (15% in hexane) followed by 73 mmol of trimethyl borate in 50 ml of THF are added dropwise. The mixture is allowed to come to −20° C., adjusted to pH=2 by addition of 2N HCl and subjected to aqueous work-up. The crude product is digested with hot heptane and crystallised at 0° C.

Step 1.4

A mixture of 60 mmol of D, 300 ml of toluene, 120 mmol of NaOH, 50 ml of water and 30 ml of 30% H₂O₂ is stirred at 45° C. for 2 hours. The mixture is adjusted to pH=2 using 10% HCl and subjected to aqueous work-up. The crude product is recrystallised from heptane.

Step 1.5

22 mmol of E are hydrogenated at 5 bar and 130° C. for 27.5 hours in 100 ml of xylene in the presence of 1.5 g of water-moist 5% Pd/C catalyst. Conventional work-up gives a colourless oil.

Step 1.6

17 mmol of BuLi (15% in hexane) are added at −70° C. to a solution of 17 mmol of 2-trimethylsilyl-1,3-dithiane in 75 ml of THF. The mixture is allowed to come to 0° C. over the course of 4 hours, then re-cooled to −70° C., 17 mmol of F in 25 ml of THF are added dropwise, and the mixture is allowed to come to room temperature, stirred for a further 18 hours and subjected to conventional aqueous work-up. The crude product is crystallised from heptane, giving colourless crystals.

Step 1.7

6.27 mmol of trifluoromethanesulfonic acid are added dropwise at −20° C. to a solution of 6.12 mmol of G in 50 ml of CH₂Cl₂. The mixture is allowed to come to room temperature for 30 minutes and then cooled to −70° C. Firstly a solution of 9.1 mmol of 3,4,5-trifluorophenol and 10.1 mmol of triethylamine in 20 l of CH₂Cl₂ and 5 minutes later 31 mmol of triethylamine tris(hydrofluoride) are then added. After a further 5 minutes, a suspension of 31.5 mmol of DBH (1,3-dibromo-5,5-dimethylhydanthoin) is added in small portions, and the mixture is stirred at −70° C. for a further 1 hour. The reaction mixture is allowed to come to −10° C. and is poured into 400 ml of ice-cold NaOH. The mixture is subjected to conventional aqueous work-up, and the crude product is purified by chromatography on silica gel (heptane/toluene 3:2) and crystallisation from pentane at −70° C., giving colourless crystals: C 35 N 66.3 l; Δn=0.0570; Δε=13.4

The following compounds of the formula

are prepared analogously:

R¹ X L¹ L² H F H H CH₃ F H H C₂H₅ F H H n-C₄H₉ F H H n-C₅H₁₁ F H H n-C₆H₁₃ F H H H F F H CH₃ F F H C₂H₅ F F H n-C₃H₇ F F H C 41 S_(B) 51 N 95.9 I; Δε = 9.7; Δn = 0.0688 n-C₄H₉ F F H C 31 S_(B) 64 N 97.1 I; Δε = 9.3; Δn = 0.0621 n-C₅H₁₁ F F H n-C₆H₁₃ F F H H F F F CH₃ F F F C 54 I; Δε = 14.8; Δn = 0.0490 C₂H₅ F F F C 48 N (34.7) I; Δε = 14.1; Δn = 0.0540 n-C₃H₇ F F F n-C₄H₉ F F F C 43 N 66.1 I; Δε = 13.3; Δn = 0.0590 n-C₅H₁₁ F F F C 39 N 75.3 I; Δε = 11.8; Δn = 0.0568 n-C₆H₁₃ F F F H Cl H H CH₃ Cl H H C₂H₅ Cl H H n-C₃H₇ Cl H H n-C₄H₉ Cl H H n-C₅H₁₁ Cl H H n-C₆H₁₃ Cl H H H Cl F H CH₃ Cl F H C₂H₅ Cl F H n-C₃H₇ Cl F H n-C₄H₉ Cl F H n-C₅H₁₁ Cl F H n-C₆H₁₃ Cl F H H Cl F F CH₃ Cl F F C₂H₅ Cl F F n-C₃H₇ Cl F F n-C₄H₉ Cl F F n-C₅H₁₁ Cl F F n-C₆H₁₃ Cl F F H OCF₃ H H CH₃ OCF₃ H H C₂H₅ OCF₃ H H n-C₃H₇ OCF₃ H H C −41 S_(B) 123 N 129.3 I; Δε = 9.1; Δn = 0.0780 n-C₄H₉ OCF₃ H H C? −54 S_(B) 129 I; Δε = 9.1; Δn = 0.0689 n-C₅H₁₁ OCF₃ H H n-C₆H₁₃ OCF₃ H H H OCF₃ F H CH₃ OCF₃ F H C₂H₅ OCF₃ F H n-C₃H₇ OCF₃ F H S_(B) 74 N 105.8 I; Δε = 11.7; Δn = 0.0701 n-C₄H₉ OCF₃ F H S_(B) 81 N 105.8 I; Δε = 11.5; Δn = 0.0623 n-C₅H₁₁ OCF₃ F H n-C₆H₁₃ OCF₃ F H H OCF₃ F F CH₃ OCF₃ F F C₂H₅ OCF₃ F F n-C₃H₇ OCF₃ F F n-C₄H₉ OCF₃ F F n-C₅H₁₁ OCF₃ F F n-C₆H₁₃ OCF₃ F F H OCHF₂ H H CH₃ OCHF₂ H H C₂H₅ OCHF₂ H H n-C₃H₇ OCHF₂ H H n-C₄H₉ OCHF₂ H H n-C₅H₁₁ OCHF₂ H H n-C₆H₁₃ OCHF₂ H H H OCHF₂ F H CH₃ OCHF₂ F H C₂H₅ OCHF₂ F H n-C₃H₇ OCHF₂ F H n-C₄H₉ OCHF₂ F H n-C₅H₁₁ OCHF₂ F H n-C₆H₁₃ OCHF₂ F H H OCHF₂ F F CH₃ OCHF₂ F F C₂H₅ OCHF₂ F F n-C₃H₇ OCHF₂ F F n-C₄H₉ OCHF₂ F F n-C₅H₁₁ OCHF₂ F F n-C₆H₁₃ OCHF₂ F F H OCHFCF₃ H H CH₃ OCHFCF₃ H H C₂H₅ OCHFCF₃ H H n-C₃H₇ OCHFCF₃ H H n-C₄H₉ OCHFCF₃ H H n-C₅H₁₁ OCHFCF₃ H H n-C₆H₁₃ OCHFCF₃ H H H OCHFCF₃ F H CH₃ OCHFCF₃ F H C₂H₅ OCHFCF₃ F H n-C₃H₇ OCHFCF₃ F H n-C₄H₉ OCHFCF₃ F H n-C₅H₁₁ OCHFCF₃ F H n-C₆H₁₃ OCHFCF₃ F H H OCHFCF₃ F F CH₃ OCHFCF₃ F F C₂H₅ OCHFCF₃ F F n-C₃H₇ OCHFCF₃ F F n-C₄H₉ OCHFCF₃ F F n-C₅H₁₁ OCHFCF₃ F F n-C₆H₁₃ OCHFCF₃ F F H OCHFCF₃ H H CH₃ OCHFCF₃ H H C₂H₅ OCHFCF₃ H H n-C₃H₇ OCHFCF₃ H H n-C₄H₉ OCHFCF₃ H H n-C₅H₁₁ OCHFCF₃ H H n-C₆H₁₃ OCHFCF₃ H H H OCHFCF₃ F H CH₃ OCHFCF₃ F H C₂H₅ OCHFCF₃ F H n-C₃H₇ OCHFCF₃ F H n-C₄H₉ OCHFCF₃ F H n-C₅H₁₁ OCHFCF₃ F H n-C₆H₁₃ OCHFCF₃ F H H OCHFCF₃ F F CH₃ OCHFCF₃ F F C₂H₅ OCHFCF₃ F F n-C₃H₇ OCHFCF₃ F F n-C₄H₉ OCHFCF₃ F F n-C₅H₁₁ OCHFCF₃ F F n-C₆H₁₃ OCHFCF₃ F F H OCF₂CHFCF₃ H H CH₃ OCF₂CHFCF₃ H H C₂H₅ OCF₂CHFCF₃ H H n-C₃H₇ OCF₂CHFCF₃ H H n-C₄H₉ OCF₂CHFCF₃ H H n-C₅H₁₁ OCF₂CHFCF₃ H H n-C₆H₁₃ OCF₂CHFCF₃ H H H OCF₂CHFCF₃ F H CH₃ OCF₂CHFCF₃ F H C₂H₅ OCF₂CHFCF₃ F H n-C₃H₇ OCF₂CHFCF₃ F H n-C₄H₉ OCF₂CHFCF₃ F H n-C₅H₁₁ OCF₂CHFCF₃ F H n-C₆H₁₃ OCF₂CHFCF₃ F H H OCF₂CHFCF₃ F F CH₃ OCF₂CHFCF₃ F F C₂H₅ OCF₂CHFCF₃ F F n-C₃H₇ OCF₂CHFCF₃ F F n-C₄H₉ OCF₂CHFCF₃ F F n-C₅H₁₁ OCF₂CHFCF₃ F F n-C₆H₁₃ OCF₂CHFCF₃ F F H NCS H H CH₃ NCS H H C₂H₅ NCS H H n-C₃H₇ NCS H H n-C₄H₉ NCS H H n-C₅H₁₁ NCS H H n-C₆H₁₃ NCS H H H NCS F H CH₃ NCS F H C₂H₅ NCS F H n-C₃H₇ NCS F H n-C₄H₉ NCS F H n-C₅H₁₁ NCS F H n-C₆H₁₃ NCS F H H NCS F F CH₃ NCS F F C₂H₅ NCS F F n-C₃H₇ NCS F F n-C₄H₉ NCS F F n-C₅H₁₁ NCS F F n-C₆H₁₃ NCS F F H C₂F₅ H H CH₃ C₂F₅ H H C₂H₅ C₂F₅ H H n-C₃H₇ C₂F₅ H H n-C₄H₉ C₂F₅ H H n-C₅H₁₁ C₂F₅ H H n-C₆H₁₃ C₂F₅ H H H C₂F₅ F H CH₃ C₂F₅ F H C₂H₅ C₂F₅ F H n-C₃H₇ C₂F₅ F H n-C₄H₉ C₂F₅ F H n-C₅H₁₁ C₂F₅ F H n-C₆H₁₃ C₂F₅ F H H C₂F₅ F F CH₃ C₂F₅ F F C₂H₅ C₂F₅ F F n-C₃H₇ C₂F₅ F F n-C₄H₉ C₂F₅ F F n-C₅H₁₁ C₂F₅ F F n-C₆H₁₃ C₂F₅ F F H C₃F₇ H H CH₃ C₃F₇ H H C₂H₅ C₃F₇ H H n-C₃H₇ C₃F₇ H H n-C₄H₉ C₃F₇ H H n-C₅H₁₁ C₃F₇ H H n-C₆H₁₃ C₃F₇ H H H C₃F₇ F H CH₃ C₃F₇ F H C₂H₅ C₃F₇ F H n-C₃H₇ C₃F₇ F H n-C₄H₉ C₃F₇ F H n-C₅H₁₁ C₃F₇ F H n-C₆H₁₃ C₃F₇ F H H C₃F₇ F F CH₃ C₃F₇ F F C₂H₅ C₃F₇ F F n-C₃H₇ C₃F₇ F F n-C₄H₉ C₃F₇ F F n-C₅H₁₁ C₃F₇ F F n-C₆H₁₃ C₃F₇ F F H SF₅ H H CH₃ SF₅ H H C₂H₅ SF₅ H H n-C₃H₇ SF₅ H H n-C₄H₉ SF₅ H H n-C₅H₁₁ SF₅ H H n-C₆H₁₃ SF₅ H H H SF₅ F H CH₃ SF₅ F H C₂H₅ SF₅ F H n-C₃H₇ SF₅ F H n-C₄H₉ SF₅ F H n-C₅H₁₁ SF₅ F H n-C₆H₁₃ SF₅ F H H SF₅ F F CH₃ SF₅ F F C₂H₅ SF₅ F F n-C₃H₇ SF₅ F F n-C₄H₉ SF₅ F F n-C₅H₁₁ SF₅ F F n-C₆H₁₃ SF₅ F F H CN H H CH₃ CN H H C₂H₅ CN H H n-C₃H₇ CN H H n-C₄H₉ CN H H n-C₅H₁₁ CN H H n-C₆H₁₃ CN H H H CN F H CH₃ CN F H C₂H₅ CN F H n-C₃H₇ CN F H n-C₄H₉ CN F H n-C₅H₁₁ CN F H n-C₆H₁₃ CN F H H CN F F CH₃ CN F F C₂H₅ CN F F n-C₃H₇ CN F F n-C₄H₉ CN F F n-C₅H₁₁ CN F F n-C₆H₁₃ CN F F

EXAMPLE 2

Step 2.1

A mixture of 50 mmol of I 50 mmol of J. 2.5 mmol of Pd(PPh₃)₄, 300 ml of toluene and 300 ml of Na borate buffer (pH=9) is stirred at 80° C. for 18 hours. The mixture is poured into 500 ml of 0.1 N HCl, and the product is extracted with CH₂Cl₂, dried over Na₂SO₄ and evaporated to dryness in a rotary evaporator. The crude product is chromatographed over silica gel in n-heptane and subsequently recrystallised twice from n-heptane at −20° C. C 78 N 93.1 l; Δn=0.1493; Δε=27.3

The following compounds of the formula

are prepared analogously:

R¹ X L¹ L² L³ L⁴ H F H H H H CH₃ F H H H H C₂H₅ F H H H H C₃H₇ F H H H H n-C₄H₉ F H H H H n-C₅H₁₁ F H H H H n-C₆H₁₃ F H H H H H F F H H H CH₃ F F H H H C₂H₅ F F H H H n-C₃H₇ F F H H H n-C₄H₉ F F H H H n-C₅H₁₁ F F H H H n-C₆H₁₃ F F H H H H F F F H H CH₃ F F F H H n-C₃H₇ F F F H H C 75 N 118.0 I; Δε = 23.2; Δn = 0.1450 n-C₄H₉ F F F H H n-C₅H₁₁ F F F H H n-C₆H₁₃ F F F H H H Cl H H H H CH₃ Cl H H H H C₂H₅ Cl H H H H n-C₃H₇ Cl H H H H n-C₄H₉ Cl H H H H n-C₅H₁₁ Cl H H H H n-C₆H₁₃ Cl H H H H H Cl F H H H CH₃ Cl F H H H C₂H₅ Cl F H H H n-C₃H₇ Cl F H H H n-C₄H₉ Cl F H H H n-C₅H₁₁ Cl F H H H n-C₆H₁₃ Cl F H H H H Cl F F H H CH₃ Cl F F H H C₂H₅ Cl F F H H n-C₃H₇ Cl F F H H n-C₄H₉ Cl F F H H n-C₅H₁₁ Cl F F H H n-C₆H₁₃ Cl F F H H H OCF₃ H H H H CH₃ OCF₃ H H H H C₂H₅ OCF₃ H H H H n-C₃H₇ OCF₃ H H H H n-C₄H₉ OCF₃ H H H H n-C₅H₁₁ OCF₃ H H H H n-C₆H₁₃ OCF₃ H H H H H OCF₃ F H H H CH₃ OCF₃ F H H H C₂H₅ OCF₃ F H H H n-C₃H₇ OCF₃ F H H H n-C₄H₉ OCF₃ F H H H n-C₅H₁₁ OCF₃ F H H H n-C₆H₁₃ OCF₃ F H H H H OCF₃ F F H H CH₃ OCF₃ F F H H C₂H₅ OCF₃ F F H H n-C₃H₇ OCF₃ F F H H n-C₄H₉ OCF₃ F F H H n-C₅H₁₁ OCF₃ F F H H n-C₆H₁₃ OCF₃ F F H H H OCHF₂ H H H H CH₃ OCHF₂ H H H H C₂H₅ OCHF₂ H H H H n-C₃H₇ OCHF₂ H H H H n-C₄H₉ OCHF₂ H H H H n-C₅H₁₁ OCHF₂ H H H H n-C₆H₁₃ OCHF₂ H H H H H OCHF₂ F H H H CH₃ OCHF₂ F H H H C₂H₅ OCHF₂ F H H H n-C₃H₇ OCHF₂ F H H H n-C₄H₉ OCHF₂ F H H H n-C₅H₁₁ OCHF₂ F H H H n-C₆H₁₃ OCHF₂ F H H H H OCHF₂ F F H H CH₃ OCHF₂ F F H H C₂H₅ OCHF₂ F F H H n-C₃H₇ OCHF₂ F F H H n-C₄H₉ OCHF₂ F F H H n-C₅H₁₁ OCHF₂ F F H H n-C₆H₁₃ OCHF₂ F F H H H OCHFCF₃ H H H H CH₃ OCHFCF₃ H H H H C₂H₅ OCHFCF₃ H H H H n-C₃H₇ OCHFCF₃ H H H H n-C₄H₉ OCHFCF₃ H H H H n-C₅H₁₁ OCHFCF₃ H H H H n-C₆H₁₃ OCHFCF₃ H H H H H OCHFCF₃ F H H H CH₃ OCHFCF₃ F H H H C₂H₅ OCHFCF₃ F H H H n-C₃H₇ OCHFCF₃ F H H H n-C₄H₉ OCHFCF₃ F H H H n-C₅H₁₁ OCHFCF₃ F H H H n-C₆H₁₃ OCHFCF₃ F H H H H OCHFCF₃ F F H H CH₃ OCHFCF₃ F F H H C₂H₅ OCHFCF₃ F F H H n-C₃H₇ OCHFCF₃ F F H H n-C₄H₉ OCHFCF₃ F F H H n-C₅H₁₁ OCHFCF₃ F F H H n-C₆H₁₃ OCHFCF₃ F F H H H OCHFCF₃ H H H H CH₃ OCHFCF₃ H H H H C₂H₅ OCHFCF₃ H H H H n-C₃H₇ OCHFCF₃ H H H H n-C₄H₉ OCHFCF₃ H H H H n-C₅H₁₁ OCHFCF₃ H H H H n-C₆H₁₃ OCHFCF₃ H H H H H OCHFCF₃ F H H H CH₃ OCHFCF₃ F H H H C₂H₅ OCHFCF₃ F H H H n-C₃H₇ OCHFCF₃ F H H H n-C₄H₉ OCHFCF₃ F H H H n-C₅H₁₁ OCHFCF₃ F H H H n-C₆H₁₃ OCHFCF₃ F H H H H OCHFCF₃ F F H H CH₃ OCHFCF₃ F F H H C₂H₅ OCHFCF₃ F F H H n-C₃H₇ OCHFCF₃ F F H H n-C₄H₉ OCHFCF₃ F F H H n-C₅H₁₁ OCHFCF₃ F F H H n-C₆H₁₃ OCHFCF₃ F F H H H OCF₂CHFCF₃ H H H H CH₃ OCF₂CHFCF₃ H H H H C₂H₅ OCF₂CHFCF₃ H H H H n-C₃H₇ OCF₂CHFCF₃ H H H H n-C₄H₉ OCF₂CHFCF₃ H H H H n-C₅H₁₁ OCF₂CHFCF₃ H H H H n-C₆H₁₃ OCF₂CHFCF₃ H H H H H OCF₂CHFCF₃ F H H H CH₃ OCF₂CHFCF₃ F H H H C₂H₅ OCF₂CHFCF₃ F H H H n-C₃H₇ OCF₂CHFCF₃ F H H H n-C₄H₉ OCF₂CHFCF₃ F H H H n-C₅H₁₁ OCF₂CHFCF₃ F H H H n-C₆H₁₃ OCF₂CHFCF₃ F H H H H OCF₂CHFCF₃ F F H H CH₃ OCF₂CHFCF₃ F F H H C₂H₅ OCF₂CHFCF₃ F F H H n-C₃H₇ OCF₂CHFCF₃ F F H H n-C₄H₉ OCF₂CHFCF₃ F F H H n-C₅H₁₁ OCF₂CHFCF₃ F F H H n-C₆H₁₃ OCF₂CHFCF₃ F F H H H NCS H H H H CH₃ NCS H H H H C₂H₅ NCS H H H H n-C₃H₇ NCS H H H H n-C₄H₉ NCS H H H H n-C₅H₁₁ NCS H H H H n-C₆H₁₃ NCS H H H H H NCS F H H H CH₃ NCS F H H H C₂H₅ NCS F H H H n-C₃H₇ NCS F H H H n-C₄H₉ NCS F H H H n-C₅H₁₁ NCS F H H H n-C₆H₁₃ NCS F H H H H NCS F F H H CH₃ NCS F F H H C₂H₅ NCS F F H H n-C₃H₇ NCS F F H H n-C₄H₉ NCS F F H H n-C₅H₁₁ NCS F F H H n-C₆H₁₃ NCS F F H H H C₂F₅ H H H H CH₃ C₂F₅ H H H H C₂H₅ C₂F₅ H H H H n-C₃H₇ C₂F₅ H H H H n-C₄H₉ C₂F₅ H H H H n-C₅H₁₁ C₂F₅ H H H H n-C₆H₁₃ C₂F₅ H H H H H C₂F₅ F H H H CH₃ C₂F₅ F H H H C₂H₅ C₂F₅ F H H H n-C₃H₇ C₂F₅ F H H H n-C₄H₉ C₂F₅ F H H H n-C₅H₁₁ C₂F₅ F H H H n-C₆H₁₃ C₂F₅ F H H H H C₂F₅ F F H H CH₃ C₂F₅ F F H H C₂H₅ C₂F₅ F F H H n-C₃H₇ C₂F₅ F F H H n-C₄H₉ C₂F₅ F F H H n-C₅H₁₁ C₂F₅ F F H H n-C₆H₁₃ C₂F₅ F F H H H C₃F₇ H H H H CH₃ C₃F₇ H H H H C₂H₅ C₃F₇ H H H H n-C₃H₇ C₃F₇ H H H H n-C₄H₉ C₃F₇ H H H H n-C₅H₁₁ C₃F₇ H H H H n-C₆H₁₃ C₃F₇ H H H H H C₃F₇ F H H H CH₃ C₃F₇ F H H H C₂H₅ C₃F₇ F H H H n-C₃H₇ C₃F₇ F H H H n-C₄H₉ C₃F₇ F H H H n-C₅H₁₁ C₃F₇ F H H H n-C₆H₁₃ C₃F₇ F H H H H C₃F₇ F F H H CH₃ C₃F₇ F F H H C₂H₅ C₃F₇ F F H H n-C₃H₇ C₃F₇ F F H H n-C₄H₉ C₃F₇ F F H H n-C₅H₁₁ C₃F₇ F F H H n-C₆H₁₃ C₃F₇ F F H H H SF₅ H H H H CH₃ SF₅ H H H H C₂H₅ SF₅ H H H H n-C₃H₇ SF₅ H H H H n-C₄H₉ SF₅ H H H H n-C₅H₁₁ SF₅ H H H H n-C₆H₁₃ SF₅ H H H H H SF₅ F H H H CH₃ SF₅ F H H H C₂H₅ SF₅ F H H H n-C₃H₇ SF₅ F H H H n-C₄H₉ SF₅ F H H H n-C₅H₁₁ SF₅ F H H H n-C₆H₁₃ SF₅ F H H H H SF₅ F F H H CH₃ SF₅ F F H H C₂H₅ SF₅ F F H H n-C₃H₇ SF₅ F F H H n-C₄H₉ SF₅ F F H H n-C₅H₁₁ SF₅ F F H H n-C₆H₁₃ SF₅ F F H H H CN H H H H CH₃ CN H H H H C₂H₅ CN H H H H n-C₃H₇ CN H H H H n-C₄H₉ CN H H H H n-C₅H₁₁ CN H H H H n-C₆H₁₃ CN H H H H H CN F H H H CH₃ CN F H H H C₂H₅ CN F H H H n-C₃H₇ CN F H H H n-C₄H₉ CN F H H H n-C₅H₁₁ CN F H H H n-C₆H₁₃ CN F H H H H CN F F H H CH₃ CN F F H H C₂H₅ CN F F H H n-C₃H₇ CN F F H H n-C₄H₉ CN F F H H n-C₅H₁₁ CN F F H H n-C₆H₁₃ CN F F H H H F H H F H CH₃ F H H F H C₂H₅ F H H F H C₃H₇ F H H F H n-C₄H₉ F H H F H n-C₅H₁₁ F H H F H n-C₆H₁₃ F H H F H H F F H F H CH₃ F F H F H C₂H₅ F F H F H n-C₃H₇ F F H F H n-C₄H₉ F F H F H n-C₅H₁₁ F F H F H n-C₆H₁₃ F F H F H H F F F F H CH₃ F F F F H C₂H₅ F F F F H C 89 N (76.8) I; Δε = 29.9; Δn = 0.1310 n-C₃H₇ F F F F H C 70 N 102.3 I; Δε = 29.7; Δn = 0.1364 n-C₄H₉ F F F F H n-C₅H₁₁ F F F F H n-C₆H₁₃ F F F F H H Cl H H F H CH₃ Cl H H F H C₂H₅ Cl H H F H n-C₃H₇ Cl H H F H n-C₄H₉ Cl H H F H n-C₅H₁₁ Cl H H F H n-C₆H₁₃ Cl H H F H H Cl F H F H CH₃ Cl F H F H C₂H₅ Cl F H F H n-C₃H₇ Cl F H F H n-C₄H₉ Cl F H F H n-C₅H₁₁ Cl F H F H n-C₆H₁₃ Cl F H F H H Cl F F F H CH₃ Cl F F F H C₂H₅ Cl F F F H n-C₃H₇ Cl F F F H n-C₄H₉ Cl F F F H n-C₅H₁₁ Cl F F F H n-C₆H₁₃ Cl F F F H H OCF₃ H H F H CH₃ OCF₃ H H F H C₂H₅ OCF₃ H H F H n-C₃H₇ OCF₃ H H F H n-C₄H₉ OCF₃ H H F H n-C₅H₁₁ OCF₃ H H F H n-C₆H₁₃ OCF₃ H H F H H OCF₃ F H F H CH₃ OCF₃ F H F H C₂H₅ OCF₃ F H F H n-C₃H₇ OCF₃ F H F H n-C₄H₉ OCF₃ F H F H n-C₅H₁₁ OCF₃ F H F H n-C₆H₁₃ OCF₃ F H F H H OCF₃ F F F H CH₃ OCF₃ F F F H C₂H₅ OCF₃ F F F H n-C₃H₇ OCF₃ F F F H n-C₄H₉ OCF₃ F F F H n-C₅H₁₁ OCF₃ F F F H n-C₆H₁₃ OCF₃ F F F H H OCHF₂ H H F H CH₃ OCHF₂ H H F H C₂H₅ OCHF₂ H H F H n-C₃H₇ OCHF₂ H H F H n-C₄H₉ OCHF₂ H H F H n-C₅H₁₁ OCHF₂ H H F H n-C₆H₁₃ OCHF₂ H H F H H OCHF₂ F H F H CH₃ OCHF₂ F H F H C₂H₅ OCHF₂ F H F H n-C₃H₇ OCHF₂ F H F H n-C₄H₉ OCHF₂ F H F H n-C₅H₁₁ OCHF₂ F H F H n-C₆H₁₃ OCHF₂ F H F H H OCHF₂ F F F H CH₃ OCHF₂ F F F H C₂H₅ OCHF₂ F F F H n-C₃H₇ OCHF₂ F F F H n-C₄H₉ OCHF₂ F F F H n-C₅H₁₁ OCHF₂ F F F H n-C₆H₁₃ OCHF₂ F F F H H OCHFCF₃ H H F H CH₃ OCHFCF₃ H H F H C₂H₅ OCHFCF₃ H H F H n-C₃H₇ OCHFCF₃ H H F H n-C₄H₉ OCHFCF₃ H H F H n-C₅H₁₁ OCHFCF₃ H H F H n-C₆H₁₃ OCHFCF₃ H H F H H OCHFCF₃ F H F H CH₃ OCHFCF₃ F H F H C₂H₅ OCHFCF₃ F H F H n-C₃H₇ OCHFCF₃ F H F H n-C₄H₉ OCHFCF₃ F H F H n-C₅H₁₁ OCHFCF₃ F H F H n-C₆H₁₃ OCHFCF₃ F H F H H OCHFCF₃ F F F H CH₃ OCHFCF₃ F F F H C₂H₅ OCHFCF₃ F F F H n-C₃H₇ OCHFCF₃ F F F H n-C₄H₉ OCHFCF₃ F F F H n-C₅H₁₁ OCHFCF₃ F F F H n-C₆H₁₃ OCHFCF₃ F F F H H OCHFCF₃ H H F H CH₃ OCHFCF₃ H H F H C₂H₅ OCHFCF₃ H H F H n-C₃H₇ OCHFCF₃ H H F H n-C₄H₉ OCHFCF₃ H H F H n-C₅H₁₁ OCHFCF₃ H H F H n-C₆H₁₃ OCHFCF₃ H H F H H OCHFCF₃ F H F H CH₃ OCHFCF₃ F H F H C₂H₅ OCHFCF₃ F H F H n-C₃H₇ OCHFCF₃ F H F H n-C₄H₉ OCHFCF₃ F H F H n-C₅H₁₁ OCHFCF₃ F H F H n-C₆H₁₃ OCHFCF₃ F H F H H OCHFCF₃ F F F H CH₃ OCHFCF₃ F F F H C₂H₅ OCHFCF₃ F F F H n-C₃H₇ OCHFCF₃ F F F H n-C₄H₉ OCHFCF₃ F F F H n-C₅H₁₁ OCHFCF₃ F F F H n-C₆H₁₃ OCHFCF₃ F F F H H OCF₂CHFCF₃ H H F H CH₃ OCF₂CHFCF₃ H H F H C₂H₅ OCF₂CHFCF₃ H H F H n-C₃H₇ OCF₂CHFCF₃ H H F H n-C₄H₉ OCF₂CHFCF₃ H H F H n-C₅H₁₁ OCF₂CHFCF₃ H H F H n-C₆H₁₃ OCF₂CHFCF₃ H H F H H OCF₂CHFCF₃ F H F H CH₃ OCF₂CHFCF₃ F H F H C₂H₅ OCF₂CHFCF₃ F H F H n-C₃H₇ OCF₂CHFCF₃ F H F H n-C₄H₉ OCF₂CHFCF₃ F H F H n-C₅H₁₁ OCF₂CHFCF₃ F H F H n-C₆H₁₃ OCF₂CHFCF₃ F H F H H OCF₂CHFCF₃ F F F H CH₃ OCF₂CHFCF₃ F F F H C₂H₅ OCF₂CHFCF₃ F F F H n-C₃H₇ OCF₂CHFCF₃ F F F H n-C₄H₉ OCF₂CHFCF₃ F F F H n-C₅H₁₁ OCF₂CHFCF₃ F F F H n-C₆H₁₃ OCF₂CHFCF₃ F F F H H NCS H H F H CH₃ NCS H H F H C₂H₅ NCS H H F H n-C₃H₇ NCS H H F H n-C₄H₉ NCS H H F H n-C₅H₁₁ NCS H H F H n-C₆H₁₃ NCS H H F H H NCS F H F H CH₃ NCS F H F H C₂H₅ NCS F H F H n-C₃H₇ NCS F H F H n-C₄H₉ NCS F H F H n-C₅H₁₁ NCS F H F H n-C₆H₁₃ NCS F H F H H NCS F F F H CH₃ NCS F F F H C₂H₅ NCS F F F H n-C₃H₇ NCS F F F H n-C₄H₉ NCS F F F H n-C₅H₁₁ NCS F F F H n-C₆H₁₃ NCS F F F H H C₂F₅ H H F H CH₃ C₂F₅ H H F H C₂H₅ C₂F₅ H H F H n-C₃H₇ C₂F₅ H H F H n-C₄H₉ C₂F₅ H H F H n-C₅H₁₁ C₂F₅ H H F H n-C₆H₁₃ C₂F₅ H H F H H C₂F₅ F H F H CH₃ C₂F₅ F H F H C₂H₅ C₂F₅ F H F H n-C₃H₇ C₂F₅ F H F H n-C₄H₉ C₂F₅ F H F H n-C₅H₁₁ C₂F₅ F H F H n-C₆H₁₃ C₂F₅ F H F H H C₂F₅ F F F H CH₃ C₂F₅ F F F H C₂H₅ C₂F₅ F F F H n-C₃H₇ C₂F₅ F F F H n-C₄H₉ C₂F₅ F F F H n-C₅H₁₁ C₂F₅ F F F H n-C₆H₁₃ C₂F₅ F F F H H C₃F₇ H H F H CH₃ C₃F₇ H H F H C₂H₅ C₃F₇ H H F H n-C₃H₇ C₃F₇ H H F H n-C₄H₉ C₃F₇ H H F H n-C₅H₁₁ C₃F₇ H H F H n-C₆H₁₃ C₃F₇ H H F H H C₃F₇ F H F H CH₃ C₃F₇ F H F H C₂H₅ C₃F₇ F H F H n-C₃H₇ C₃F₇ F H F H n-C₄H₉ C₃F₇ F H F H n-C₅H₁₁ C₃F₇ F H F H n-C₆H₁₃ C₃F₇ F H F H H C₃F₇ F F F H CH₃ C₃F₇ F F F H C₂H₅ C₃F₇ F F F H n-C₃H₇ C₃F₇ F F F H n-C₄H₉ C₃F₇ F F F H n-C₅H₁₁ C₃F₇ F F F H n-C₆H₁₃ C₃H₇ F F F H H SF₅ H H F H CH₃ SF₅ H H F H C₂H₅ SF₅ H H F H n-C₃H₇ SF₅ H H F H n-C₄H₉ SF₅ H H F H n-C₅H₁₁ SF₅ H H F H n-C₆H₁₃ SF₅ H H F H H SF₅ F H F H CH₃ SF₅ F H F H C₂H₅ SF₅ F H F H n-C₃H₇ SF₅ F H F H n-C₄H₉ SF₅ F H F H n-C₅H₁₁ SF₅ F H F H n-C₆H₁₃ SF₅ F H F H H SF₅ F F F H CH₃ SF₅ F F F H C₂H₅ SF₅ F F F H n-C₃H₇ SF₅ F F F H n-C₄H₉ SF₅ F F F H n-C₅H₁₁ SF₅ F F F H n-C₆H₁₃ SF₅ F F F H H CN H H F H CH₃ CN H H F H C₂H₅ CN H H F H n-C₃H₇ CN H H F H n-C₄H₉ CN H H F H n-C₅H₁₁ CN H H F H n-C₆H₁₃ CN H H F H H CN F H F H CH₃ CN F H F H C₂H₅ CN F H F H n-C₃H₇ CN F H F H n-C₄H₉ CN F H F H n-C₅H₁₁ CN F H F H n-C₆H₁₃ CN F H F H H CN F F F H CH₃ CN F F F H C₂H₅ CN F F F H n-C₃H₇ CN F F F H n-C₄H₉ CN F F F H n-C₅H₁₁ CN F F F H n-C₆H₁₃ CN F F F H H F H H F F CH₃ F H H F F C₂H₅ F H H F F n-C₄H₉ F H H F F n-C₅H₁₁ F H H F F n-C₆H₁₃ F H H F F H F F H F F CH₃ F F H F F C₂H₅ F F H F F n-C₃H₇ F F H F F n-C₄H₉ F F H F F n-C₅H₁₁ F F H F F n-C₆H₁₃ F F H F F H F F F F F CH₃ F F F F F C₂H₅ F F F F F C₂H₅ F F F F F C 91 N (58.8) I; Δε = 35.0; Δn = 0.1149 n-C₃H₇ F F F F F C 83 N (83.0) I; Δε = 34.9; Δn = 0.1231 n-C₄H₉ F F F F F C 90 N 79.4 I; Δε = 32.4; Δn = 0.1171 n-C₅H₁₁ F F F F F C 82 N 84.3 I; Δε = 31.9; Δn = 0.1205 n-C₆H₁₃ F F F F F C 89 N (83.4) I; Δε = 30.6; Δn = 0.1116 n-C₇H₁₅ F F F F F C 82 N 84.3 I; Δε = 30.3; Δn = 0.1130 H Cl H H F F CH₃ Cl H H F F C₂H₅ Cl H H F F n-C₃H₇ Cl H H F F n-C₄H₉ Cl H H F F n-C₅H₁₁ Cl H H F F n-C₆H₁₃ Cl H H F F H Cl F H F F CH₃ Cl F H F F C₂H₅ Cl F H F F n-C₃H₇ Cl F H F F n-C₄H₉ Cl F H F F n-C₅H₁₁ Cl F H F F n-C₆H₁₃ Cl F H F F H Cl F F F F CH₃ Cl F F F F C₂H₅ Cl F F F F n-C₃H₇ Cl F F F F C 80 N 106.7 I; Δε = 31.5; Δn = 0.1372 n-C₄H₉ Cl F F F F n-C₅H₁₁ Cl F F F F n-C₆H₁₃ Cl F F F F H OCF₃ H H F F CH₃ OCF₃ H H F F C₂H₅ OCF₃ H H F F n-C₃H₇ OCF₃ H H F F C 80 N 119.8 I; Δε = 25.3; Δn = 0.1330 n-C₄H₉ OCF₃ H H F F n-C₅H₁₁ OCF₃ H H F F n-C₆H₁₃ OCF₃ H H F F H OCF₃ F H F F CH₃ OCF₃ F H F F C₂H₅ OCF₃ F H F F n-C₃H₇ OCF₃ F H F F C 48 S_(A) (46) N 105.1 I; Δε = 29.8; Δn = 0.1180 n-C₄H₉ OCF₃ F H F F n-C₅H₁₁ OCF₃ F H F F n-C₆H₁₃ OCF₃ F H F F H OCF₃ F F F F CH₃ OCF₃ F F F F C₂H₅ OCF₃ F F F F n-C₃H₇ OCF₃ F F F F C 73 N 97.5 I; Δε = 35.6; Δn = 0.1158 n-C₄H₉ OCF₃ F F F F n-C₅H₁₁ OCF₃ F F F F n-C₆H₁₃ OCF₃ F F F F H OCHF₂ H H F F CH₃ OCHF₂ H H F F C₂H₅ OCHF₂ H H F F n-C₃H₇ OCHF₂ H H F F n-C₄H₉ OCHF₂ H H F F n-C₅H₁₁ OCHF₂ H H F F n-C₆H₁₃ OCHF₂ H H F F H OCHF₂ F H F F CH₃ OCHF₂ F H F F C₂H₅ OCHF₂ F H F F n-C₃H₇ OCHF₂ F H F F n-C₄H9 OOHF₂ F H F F n-C₅H₁₁ OCHF₂ F H F F n-C₆H₁₃ OCHF₂ F H F F H OCHF₂ F F F F CH₃ OCHF₂ F F F F C₂H₅ OCHF₂ F F F F n-C₃H₇ OCHF₂ F F F F n-C₄H₉ OCHF₂ F F F F n-C₅H₁₁ OCHF₂ F F F F n-C₆H₁₃ OCHF₂ F F F F H OCHFCF₃ H H F F CH₃ OCHFCF₃ H H F F C₂H₅ OCHFCF₃ H H F F n-C₃H₇ OCHFCF₃ H H F F n-C₄H₉ OCHFCF₃ H H F F n-C₅H₁₁ OCHFCF₃ H H F F n-C₆H₁₃ OCHFCF₃ H H F F H OCHFCF₃ F H F F CH₃ OCHFCF₃ F H F F C₂H₅ OCHFCF₃ F H F F n-C₃H₇ OCHFCF₃ F H F F n-C₄H₉ OCHFCF₃ F H F F n-C₅H₁₁ OCHFCF₃ F H F F n-C₆H₁₃ OCHFCF₃ F H F F H OCHFCF₃ F F F F CH₃ OCHFCF₃ F F F F C₂H₅ OCHFCF₃ F F F F n-C₃H₇ OCHFCF₃ F F F F n-C₄H₉ OCHFCF₃ F F F F n-C₅H₁₁ OCHFCF₃ F F F F n-C₆H₁₃ OCHFCF₃ F F F F H OCHFCF₃ H H F F CH₃ OCHFCF₃ H H F F C₂H₅ OCHFCF₃ H H F F n-C₃H₇ OCHFCF₃ H H F F n-C₄H₉ OCHFCF₃ H H F F n-C₅H₁₁ OCHFCF₃ H H F F n-C₆H₁₃ OCHFCF₃ H H F F H OCHFCF₃ F H F F CH₃ OCHFCF₃ F H F F C₂H₅ OCHFCF₃ F H F F n-C₃H₇ OCHFCF₃ F H F F n-C₄H₉ OCHFCF₃ F H F F n-C₅H₁₁ OCHFCF₃ F H F F n-C₆H₁₃ OCHFCF₃ F H F F H OCHFCF₃ F F F F CH₃ OCHFCF₃ F F F F C₂H₅ OCHFCF₃ F F F F n-C₃H₇ OCHFCF₃ F F F F n-C₄H₉ OCHFCF₃ F F F F n-C₅H₁₁ OCHFCF₃ F F F F n-C₆H₁₃ OCHFCF₃ F F F F H OCF₂CHFCF₃ H H F F CH₃ OCF₂CHFCF₃ H H F F C₂H₅ OCF₂CHFCF₃ H H F F n-C₃H₇ OCF₂CHFCF₃ H H F F n-C₄H₉ OCF₂CHFCF₃ H H F F n-C₅H₁₁ OCF₂CHFCF₃ H H F F n-C₆H₁₃ OCF₂CHFCF₃ H H F F H OCF₂CHFCF₃ F H F F CH₃ OCF₂CHFCF₃ F H F F C₂H₅ OCF₂CHFCF₃ F H F F n-C₃H₇ OCF₂CHFCF₃ F H F F n-C₄H₉ OCF₂CHFCF₃ F H F F n-C₅H₁₁ OCF₂CHFCF₃ F H F F n-C₆H₁₃ OCF₂CHFCF₃ F H F F H OCF₂CHFCF₃ F F F F CH₃ OCF₂CHFCF₃ F F F F C₂H₅ OCF₂CHFCF₃ F F F F n-C₃H₇ OCF₂CHFCF₃ F F F F n-C₄H₉ OCF₂CHFCF₃ F F F F n-C₅H₁₁ OCF₂CHFCF₃ F F F F n-C₆H₁₃ OCF₂CHFCF₃ F F F F H NCS H H F F CH₃ NCS H H F F C₂H₅ NCS H H F F n-C₃H₇ NCS H H F F C 107 N 185.5 I; Δε = 31.4; Δn = 0.2052 n-C₄H₉ NCS H H F F n-C₅H₁₁ NCS H H F F n-C₆H₁₃ NCS H H F F H NCS F H F F CH₃ NCS F H F F C₂H₅ NCS F H F F n-C₃H₇ NCS F H F F n-C₄H₉ NCS F H F F n-C₅H₁₁ NCS F H F F n-C₆H₁₃ NCS F H F F H NCS F F F F CH₃ NCS F F F F C₂H₅ NCS F F F F n-C₃H₇ NCS F F F F n-C₄H₉ NCS F F F F n-C₅H₁₁ NCS F F F F n-C₆H₁₃ NCS F F F F H C₂F₅ H H F F CH₃ C₂F₅ H H F F C₂H₅ C₂F₅ H H F F n-C₃H₇ C₂F₅ H H F F n-C₄H₉ C₂F₅ H H F F n-C₅H₁₁ C₂F₅ H H F F n-C₆H₁₃ C₂F₅ H H F F H C₂F₅ F H F F CH₃ C₂F₅ F H F F C₂H₅ C₂F₅ F H F F n-C₃H₇ C₂F₅ F H F F n-C₄H₉ C₂F₅ F H F F n-C₅H₁₁ C₂F₅ F H F F n-C₆H₁₃ C₂F₅ F H F F H C₂F₅ F F F F CH₃ C₂F₅ F F F F C₂H₅ C₂F₅ F F F F n-C₃H₇ C₂F₅ F F F F n-C₄H₉ C₂F₅ F F F F n-C₅H₁₁ C₂F₅ F F F F n-C₆H₁₃ C₂F₅ F F F F H C₃F₇ H H F F CH₃ C₃F₇ H H F F C₂H₅ C₃F₇ H H F F n-C₃H₇ C₃F₇ H H F F n-C₄H₉ C₃F₇ H H F F n-C₅H₁₁ C₃F₇ H H F F n-C₆H₁₃ C₃F₇ H H F F H C₃F₇ F H F F CH₃ C₃F₇ F H F F C₂H₅ C₃F₇ F H F F n-C₃H₇ C₃F₇ F H F F n-C₄H₉ C₃F₇ F H F F n-C₅H₁₁ C₃F₇ F H F F n-C₆H₁₃ C₃F₇ F H F F H C₃F₇ F F F F CH₃ C₃F₇ F F F F C₂H₅ C₃F₇ F F F F n-C₃H₇ C₃F₇ F F F F n-C₄H₉ C₃F₇ F F F F n-C₅H₁₁ C₃F₇ F F F F n-C₆H₁₃ C₃F₇ F F F F H SF₅ H H F F CH₃ SF₅ H H F F C₂H₅ SF₅ H H F F n-C₃H₇ SF₅ H H F F n-C₄H₉ SF₅ H H F F n-C₅H₁₁ SF₅ H H F F n-C₆H₁₃ SF₅ H H F F H SF₅ F H F F CH₃ SF₅ F H F F C₂H₅ SF₅ F H F F n-C₃H₇ SF₅ F H F F n-C₄H₉ SF₅ F H F F n-C₅H₁₁ SF₅ F H F F n-C₆H₁₃ SF₅ F H F F H SF₅ F F F F CH₃ SF₅ F F F F C₂H₅ SF₅ F F F F n-C₃H₇ SF₅ F F F F C 110 N (83.4) I; Δε = 33.8; Δn = 0.1211 n-C₄H₉ SF₅ F F F F n-C₅H₁₁ SF₅ F F F F n-C₆H₁₃ SF₅ F F F F H CN H H F F CH₃ CN H H F F C₂H₅ CN H H F F n-C₃H₇ CN H H F F n-C₄H₉ CN H H F F n-C₅H₁₁ CN H H F F n-C₆H₁₃ CN H H F F H CN F H F F CH₃ CN F H F F C₂H₅ CN F H F F n-C₃H₇ CN F H F F n-C₄H₉ CN F H F F n-C₅H₁₁ CN F H F F n-C₆H₁₃ CN F H F F H CN F F F F CH₃ CN F F F F C₂H₅ CN F F F F C 98 N_(Re) (71) S_(C) (84) N 127.6 I Δε = 67.8; Δn = 0.1459 n-C₃H₇ CN F F F F C 75 S_(c)? (65) N 144.1 I Δn = 0.1561; Δε = 66.5 n-C₄H₉ CN F F F F C 79 N 139.3 I; Δε = 64.2; Δn = 0.1477 n-C₅H₁₁ CN F F F F C 65 S_(C) (44) N 141.5 I; Δε = 61.8; Δn = 0.1490 n-C₆H₁₃ CN F F F F n-C₇H₁₅ CN F F F F C 51 N 130.8 I; Δε = 58.4; Δn = 0.1459 H CF₃ H H F F C₂H₅ CF₃ H H F F n-C₃H₇ CF₃ H H F F C 95 N (87.5) I; Δε = 31.5; Δn = 0.1330 n-C₄H₉ CF₃ H H F F n-C₅H₁₁ CF₃ H H F F n-C₆H₁₃ CF₃ H H F F CH₂═CH CF₃ H H F F H CF₃ F F F F C₂H₅ CF₃ F F F F n-C₃H₇ CF₃ F F F F C 91 I; Δn = 0.1190; Δε = 40.8 n-C₄H₉ CF₃ F F F F n-C₅H₁₁ CF₃ F F F F n-C₆H₁₃ CF₃ F F F F CH₂═CH CF₃ F F F F H F H H F F C₂H₅ F H H F F n-C₃H₇ F H H F F n-C₄H₉ F H H F F n-C₅H₁₁ F H H F F n-C₆H₁₃ F H H F F CH₂═CH F H H F F

EXAMPLE 3

Step 3.1

62.7 mmol of trifluoromethanesulfonic acid are added dropwise at −20° C. to a solution of 61.2 mmol of L in 500 ml of CH₂Cl₂. The mixture is allowed to come to room, temperature for 30 minutes and then cooled to −70° C. Firstly a solution of 91 mmol of 4-bromo-3-fluorophenol and 101 mmol of triethylamine in 200 ml of CH₂Cl₂ and 5 minutes later 310 mmol of triethylamine tris(hydrofluoride) are then added. After a further 5 minutes, a suspension of 315 mmol of 1,3-dibromo-5,5-dimethylhydanthoin is added in small portions, and the mixture is stirred at −70° C. for a further 1 hour. The reaction mixture is allowed to come to −10° C. and is poured into ice-cold NaOH. The mixture is subjected to conventional aqueous work-up, and the crude product is purified by chromatography on silica gel (heptane/MTB ether 4:1) and crystallisation from ethanol at −20° C.

Step 3.2

A mixture of 50 mmol of M, 50 mmol of 3,4,5-trifluorobenzeneboronic acid, 2.5 mmol of Pd(PPh₃)₄, 300 ml of toluene and 300 ml of Na borate buffer (pH=9) is stirred at 80° C. for 18 hours. The mixture is poured into 500 ml of 0.1 N HCl, and the product is extracted with CH₂Cl₂, dried over Na₂SO₄ and evaporated to dryness in a rotary evaporator. The crude product is chromatographed over silica gel in n-heptane and subsequently recrystallised from n-heptane at −20° C. C 61 N 191.8 l; Δn=0.1220; Δε=19.1

The following compounds of the formula

are prepared analogously:

R¹ X L¹ L² H F H H CH₃ F H H C₂H₅ F H H n-C₃H₇ F H H C 84 N 232.4 I; Δε = 9.4; Δn = 0.1390 n-C₄H₉ F H H n-C₅H₁₁ F H H n-C₆H₁₃ F H H H F F H CH₃ F F H C₂H₅ F F H n-C₃H₇ F F H C 44 S_(M)? 45 N 212.6 I; Δε = 13.4; Δn = 0.1328 n-C₄H₉ F F H n-C₅H₁₁ F F H n-C₆H₁₃ F F H H F F F CH₃ F F F C₂H₅ F F F n-C₄H₉ F F F n-C₅H₁₁ F F F n-C₆H₁₃ F F F H Cl H H CH₃ Cl H H C₂H₅ Cl H H n-C₃H₇ Cl H H n-C₄H₉ Cl H H n-C₅H₁₁ Cl H H n-C₆H₁₃ Cl H H H Cl F H CH₃ Cl F H C₂H₅ Cl F H n-C₃H₇ Cl F H n-C₄H₉ Cl F H n-C₅H₁₁ Cl F H n-C₆H₁₃ Cl F H H Cl F F CH₃ Cl F F C₂H₅ Cl F F n-C₃H₇ Cl F F n-C₄H₉ Cl F F n-C₅H₁₁ Cl F F n-C₆H₁₃ Cl F F H OCF₃ H H CH₃ OCF₃ H H C₂H₅ OCF₃ H H n-C₃H₇ OCF₃ H H n-C₄H₉ OCF₃ H H n-C₅H₁₁ OCF₃ H H n-C₆H₁₃ OCF₃ H H H OCF₃ F H CH₃ OCF₃ F H C₂H₅ OCF₃ F H n-C₃H₇ OCF₃ F H n-C₄H₉ OCF₃ F H n-C₅H₁₁ OCF₃ F H n-C₆H₁₃ OCF₃ F H H OCF₃ F F CH₃ OCF₃ F F C₂H₅ OCF₃ F F n-C₃H₇ OCF₃ F F n-C₄H₉ OCF₃ F F n-C₅H₁₁ OCF₃ F F n-C₆H₁₃ OCF₃ F F H OCHF₂ H H CH₃ OCHF₂ H H C₂H₅ OCHF₂ H H n-C₃H₇ OCHF₂ H H n-C₄H₉ OCHF₂ H H n-C₅H₁₁ OCHF₂ H H n-C₆H₁₃ OCHF₂ H H H OCHF₂ F H CH₃ OCHF₂ F H C₂H₅ OCHF₂ F H n-C₃H₇ OCHF₂ F H n-C₄H₉ OCHF₂ F H n-C₅H₁₁ OCHF₂ F H n-C₆H₁₃ OCHF₂ F H H OCHF₂ F F CH₃ OCHF₂ F F C₂H₅ OCHF₂ F F n-C₃H₇ OCHF₂ F F n-C₄H₉ OCHF₂ F F n-C₅H₁₁ OCHF₂ F F n-C₆H₁₃ OCHF₂ F F H OCHFCF₃ H H CH₃ OCHFCF₃ H H C₂H₅ OCHFCF₃ H H n-C₃H₇ OCHFCF₃ H H n-C₄H₉ OCHFCF₃ H H n-C₅H₁₁ OCHFCF₃ H H n-C₆H₁₃ OCHFCF₃ H H H OCHFCF₃ F H CH₃ OCHFCF₃ F H C₂H₅ OCHFCF₃ F H n-C₃H₇ OCHFCF₃ F H n-C₄H₉ OCHFCF₃ F H n-C₅H₁₁ OCHFCF₃ F H n-C₆H₁₃ OCHFCF₃ F H H OCHFCF₃ F F CH₃ OCHFCF₃ F F C₂H₅ OCHFCF₃ F F n-C₃H₇ OCHFCF₃ F F n-C₄H₉ OCHFCF₃ F F n-C₅H₁₁ OCHFCF₃ F F n-C₆H₁₃ OCHFCF₃ F F H OCHFCF₃ H H CH₃ OCHFCF₃ H H C₂H₅ OCHFCF₃ H H n-C₃H₇ OCHFCF₃ H H n-C₄H₉ OCHFCF₃ H H n-C₅H₁₁ OCHFCF₃ H H n-C₆H₁₃ OCHFCF₃ H H H OCHFCF₃ F H CH₃ OCHFCF₃ F H C₂H₅ OCHFCF₃ F H n-C₃H₇ OCHFCF₃ F H n-C₄H₉ OCHFCF₃ F H n-C₅H₁₁ OCHFCF₃ F H n-C₆H₁₃ OCHFCF₃ F H H OCHFCF₃ F F CH₃ OCHFCF₃ F F C₂H₅ OCHFCF₃ F F n-C₃H₇ OCHFCF₃ F F n-C₄H₉ OCHFCF₃ F F n-C₅H₁₁ OCHFCF₃ F F n-C₆H₁₃ OCHFCF₃ F F H OCF₂CHFCF₃ H H CH₃ OCF₂CHFCF₃ H H C₂H₅ OCF₂CHFCF₃ H H n-C₃H₇ OCF₂CHFCF₃ H H n-C₄H₉ OCF₂CHFCF₃ H H n-C₅H₁₁ OCF₂CHFCF₃ H H n-C₆H₁₃ OCF₂CHFCF₃ H H H OCF₂CHFCF₃ F H CH₃ OCF₂CHFCF₃ F H C₂H₅ OCF₂CHFCF₃ F H n-C₃H₇ OCF₂CHFCF₃ F H n-C₄H₉ OCF₂CHFCF₃ F H n-C₅H₁₁ OCF₂CHFCF₃ F H n-C₆H₁₃ OCF₂CHFCF₃ F H H OCF₂CHFCF₃ F F CH₃ OCF₂CHFCF₃ F F C₂H₅ OCF₂CHFCF₃ F F n-C₃H₇ OCF₂CHFCF₃ F F n-C₄H₉ OCF₂CHFCF₃ F F n-C₅H₁₁ OCF₂CHFCF₃ F F n-C₆H₁₃ OCF₂CHFCF₃ F F H NCS H H CH₃ NCS H H C₂H₅ NCS H H n-C₃H₇ NCS H H n-C₄H₉ NCS H H n-C₅H₁₁ NCS H H n-C₆H₁₃ NCS H H H NCS F H CH₃ NCS F H C₂H₅ NCS F H n-C₃H₇ NCS F H n-C₄H₉ NCS F H n-C₅H₁₁ NCS F H n-C₆H₁₃ NCS F H H NCS F F CH₃ NCS F F C₂H₅ NCS F F n-C₃H₇ NCS F F n-C₄H₉ NCS F F n-C₅H₁₁ NCS F F n-C₆H₁₃ NCS F F H C₂F₅ H H CH₃ C₂F₅ H H C₂H₅ C₂F₅ H H n-C₃H₇ C₂F₅ H H n-C₄H₉ C₂F₅ H H n-C₅H₁₁ C₂F₅ H H n-C₆H₁₃ C₂F₅ H H H C₂F₅ F H CH₃ C₂F₅ F H C₂H₅ C₂F₅ F H n-C₃H₇ C₂F₅ F H n-C₄H₉ C₂F₅ F H n-C₅H₁₁ C₂F₅ F H n-C₆H₁₃ C₂F₅ F H H C₂F₅ F F CH₃ C₂F₅ F F C₂H₅ C₂F₅ F F n-C₃H₇ C₂F₅ F F n-C₄H₉ C₂F₅ F F n-C₅H₁₁ C₂F₅ F F n-C₆H₁₃ C₂F₅ F F H C₃F₇ H H CH₃ C₃F₇ H H C₂H₅ C₃F₇ H H n-C₃H₇ C₃F₇ H H n-C₄H₉ C₃F₇ H H n-C₅H₁₁ C₃F₇ H H n-C₆H₁₃ C₃F₇ H H H C₃F₇ F H CH₃ C₃F₇ F H C₂H₅ C₃F₇ F H n-C₃H₇ C₃F₇ F H n-C₄H₉ C₃F₇ F H n-C₅H₁₁ C₃F₇ F H n-C₆H₁₃ C₃F₇ F H H C₃H₇ F F CH₃ C₃F₇ F F C₂H₅ C₃F₇ F F n-C₃H₇ C₃F₇ F F n-C₄H₉ C₃F₇ F F n-C₅H₁₁ C₃F₇ F F n-C₆H₁₃ C₃F₇ F F H SF₅ H H CH₃ SF₅ H H C₂H₅ SF₅ H H n-C₃H₇ SF₅ H H n-C₄H₉ SF₅ H H n-C₅H₁₁ SF₅ H H n-C₆H₁₃ SF₅ H H H SF₅ F H CH₃ SF₅ F H C₂H₅ SF₅ F H n-C₃H₇ SF₅ F H n-C₄H₉ SF₅ F H n-C₅H₁₁ SF₅ F H n-C₆H₁₃ SF₅ F H H SF₅ F F CH₃ SF₅ F F C₂H₅ SF₅ F F n-C₃H₇ SF₅ F F n-C₄H₉ SF₅ F F n-C₅H₁₁ SF₅ F F n-C₆H₁₃ SF₅ F F H CN H H CH₃ CN H H C₂H₅ CN H H n-C₃H₇ CN H H n-C₄H₉ CN H H n-C₅H₁₁ CN H H n-C₆H₁₃ CN H H H CN F H CH₃ CN F H C₂H₅ CN F H n-C₃H₇ CN F H n-C₄H₉ CN F H

EXAMPLE 4

Step 4.1

62.7 mmol of trifluoromethanesulfonic acid are added dropwise at −20° C. to a solution of 61.2 mmol of N in 500 ml of CH₂Cl₂.The mixture is allowed to come to room temperature for 30 minutes and is then cooled to −70° C. Then, firstly a solution of 91 mmol of 4-bromophenol and 101 mmol of triethylamine in 200 ml of CH₂Cl₂ and, 5 minutes later, 310 mmol of triethylamine tris(hydrofluoride) are added. After a further 5 minutes, a suspension of 315 mmol of 1,3-dibromo-5,5-dimethylhydanthoin is added in small portions, and the mixture is stirred at −70° C. for a further 1 hour. The reaction mixture is allowed to come to −10° C. and is poured into ice-cold NaOH. The mixture is subjected to conventional aqueous work-up, and the crude product is purified by chromatography on silica gel (heptane/MTB ether 4:1) and crystallization from ethanol at −20° C.

Step 4.2

A mixture of 50 mmol of O, 50 mmol of 3,4,5-trifluorobenzeneboronic acid, 2.5 mmol of Pd(PPh₃)₄, 300 ml of toluene and 300 ml of Na borate buffer (pH=9) is stirred at 80° C. for 18 hours. The mixture is poured into 500 ml of 0.1 N HCl, the product is extracted with CH₂Cl₂, and the extracts are dried over Na₂SO₄ and evaporated to dryness in a rotary evaporator. The crude product is chromatographed over silica gel in n-heptane and subsequently recrystallized from n-heptane at −20° C. C 60 S_(B) 81 N 206.6 l; Δn=0.1291; Δε=15.7

The following compounds of the formula

are prepared analogously:

R¹ X L¹ L² H F H H CH₃ F H H C₂H₅ F H H n-C₃H₇ F H H n-C₄H₉ F H H n-C₅H₁₁ F H H n-C₆H₁₃ F H H H F F H CH₃ F F H C₂H₅ F F H n-C₃H₇ F F H C 47 S_(B) 91 N 238.0 I; Δε = 10.7; Δn = 0.1370 n-C₄H₉ F F H n-C₅H₁₁ F F H n-C₆H₁₃ F F H H F F F CH₃ F F F C₂H₅ F F F n-C₄H₉ F F F n-C₅H₁₁ F F F n-C₆H₁₃ F F F H Cl H H CH₃ Cl H H C₂H₅ Cl H H n-C₃H₇ Cl H H n-C₄H₉ Cl H H n-C₅H₁₁ Cl H H n-C₆H₁₃ Cl H H H Cl F H CH₃ Cl F H C₂H₅ Cl F H n-C₃H₇ Cl F H n-C₄H₉ Cl F H n-C₅H₁₁ Cl F H n-C₆H₁₃ Cl F H H Cl F F CH₃ Cl F F C₂H₅ Cl F F n-C₃H₇ Cl F F n-C₄H₉ Cl F F n-C₅H₁₁ Cl F F n-C₆H₁₃ Cl F F H OCF₃ H H CH₃ OCF₃ H H C₂H₅ OCF₃ H H n-C₃H₇ OCF₃ H H n-C₄H₉ OCF₃ H H n-C₅H₁₁ OCF₃ H H n-C₆H₁₃ OCF₃ H H H OCF₃ F H CH₃ OCF₃ F H C₂H₅ OCF₃ F H n-C₃H₇ OCF₃ F H n-C₄H₉ OCF₃ F H n-C₅H₁₁ OCF₃ F H n-C₆H₁₃ OCF₃ F H H OCF₃ F F CH₃ OCF₃ F F C₂H₅ OCF₃ F F n-C₃H₇ OCF₃ F F n-C₄H₉ OCF₃ F F n-C₅H₁₁ OCF₃ F F n-C₆H₁₃ OCF₃ F F H OCHF₂ H H CH₃ OCHF₂ H H C₂H₅ OCHF₂ H H n-C₃H₇ OCHF₂ H H n-C₄H₉ OCHF₂ H H n-C₅H₁₁ OCHF₂ H H n-C₆H₁₃ OCHF₂ H H H OCHF₂ F H CH₃ OCHF₂ F H C₂H₅ OCHF₂ F H n-C₃H₇ OCHF₂ F H n-C₄H₉ OCHF₂ F H n-C₅H₁₁ OCHF₂ F H n-C₆H₁₃ OCHF₂ F H H OCHF₂ F F CH₃ OCHF₂ F F C₂H₅ OCHF₂ F F n-C₃H₇ OCHF₂ F F n-C₄H₉ OCHF₂ F F n-C₅H₁₁ OCHF₂ F F n-C₆H₁₃ OCHF₂ F F H OCHFCF₃ H H CH₃ OCHFCF₃ H H C₂H₅ OCHFCF₃ H H n-C₃H₇ OCHFCF₃ H H n-C₄H₉ OCHFCF₃ H H n-C₅H₁₁ OCHFCF₃ H H n-C₆H₁₃ OCHFCF₃ H H H OCHFCF₃ F H CH₃ OCHFCF₃ F H C₂H₅ OCHFCF₃ F H n-C₃H₇ OCHFCF₃ F H n-C₄H₉ OCHFCF₃ F H n-C₅H₁₁ OCHFCF₃ F H n-C₆H₁₃ OCHFCF₃ F H H OCHFCF₃ F F CH₃ OCHFCF₃ F F C₂H₅ OCHFCF₃ F F n-C₃H₇ OCHFCF₃ F F n-C₄H₉ OCHFCF₃ F F n-C₅H₁₁ OCHFCF₃ F F n-C₆H₁₃ OCHFCF₃ F F H OCHFCF₃ H H CH₃ OCHFCF₃ H H C₂H₅ OCHFCF₃ H H n-C₃H₇ OCHFCF₃ H H n-C₄H₉ OCHFCF₃ H H n-C₅H₁₁ OCHFCF₃ H H n-C₆H₁₃ OCHFCF₃ H H H OCHFCF₃ F H CH₃ OCHFCF₃ F H C₂H₅ OCHFCF₃ F H n-C₃H₇ OCHFCF₃ F H n-C₄H₉ OCHFCF₃ F H n-C₅H₁₁ OCHFCF₃ F H n-C₆H₁₃ OCHFCF₃ F H H OCHFCF₃ F F CH₃ OCHFCF₃ F F C₂H₅ OCHFCF₃ F F n-C₃H₇ OCHFCF₃ F F n-C₄H₉ OCHFCF₃ F F n-C₅H₁₁ OCHFCF₃ F F n-C₆H₁₃ OCHFCF₃ F F H OCF₂CHFCF₃ H H CH₃ OCF₂CHFCF₃ H H C₂H₅ OCF₂CHFCF₃ H H n-C₃H₇ OCF₂CHFCF₃ H H n-C₄H₉ OCF₂CHFCF₃ H H n-C₅H₁₁ OCF₂CHFCF₃ H H n-C₆H₁₃ OCF₂CHFCF₃ H H H OCF₂CHFCF₃ F H CH₃ OCF₂CHFCF₃ F H C₂H₅ OCF₂CHFCF₃ F H n-C₃H₇ OCF₂CHFCF₃ F H n-C₄H₉ OCF₂CHFCF₃ F H n-C₅H₁₁ OCF₂CHFCF₃ F H n-C₆H₁₃ OCF₂CHFCF₃ F H H OCF₂CHFCF₃ F F CH₃ OCF₂CHFCF₃ F F C₂H₅ OCF₂CHFCF₃ F F n-C₃H₇ OCF₂CHFCF₃ F F n-C₄H₉ OCF₂CHFCF₃ F F n-C₅H₁₁ OCF₂CHFCF₃ F F n-C₆H₁₃ OCF₂CHFCF₃ F F H NCS H H CH₃ NCS H H C₂H₅ NCS H H n-C₃H₇ NCS H H n-C₄H₉ NCS H H n-C₅H₁₁ NCS H H n-C₆H₁₃ NCS H H H NCS F H CH₃ NCS F H C₂H₅ NCS F H n-C₃H₇ NCS F H n-C₄H₉ NCS F H n-C₅H₁₁ NCS F H n-C₆H₁₃ NCS F H H NCS F F CH₃ NCS F F C₂H₅ NCS F F n-C₃H₇ NCS F F n-C₄H₉ NCS F F n-C₅H₁₁ NCS F F n-C₆H₁₃ NCS F F H C₂F₅ H H CH₃ C₂F₅ H H C₂H₅ C₂F₅ H H n-C₃H₇ C₂F₅ H H n-C₄H₉ C₂F₅ H H n-C₅H₁₁ C₂F₅ H H n-C₆H₁₃ C₂F₅ H H H C₂F₅ F H CH₃ C₂F₅ F H C₂H₅ C₂F₅ F H n-C₃H₇ C₂F₅ F H n-C₄H₉ C₂F₅ F H n-C₅H₁₁ C₂F₅ F H n-C₆H₁₃ C₂F₅ F H H C₂F₅ F F CH₃ C₂F₅ F F C₂H₅ C₂F₅ F F n-C₃H₇ C₂F₅ F F n-C₄H₉ C₂F₅ F F n-C₅H₁₁ C₂F₅ F F n-C₆H₁₃ C₂F₅ F F H C₃F₇ H H CH₃ C₃F₇ H H C₂H₅ C₃F₇ H H n-C₃H₇ C₃F₇ H H n-C₄H₉ C₃F₇ H H n-C₅H₁₁ C₃F₇ H H n-C₆H₁₃ C₃F₇ H H H C₃F₇ F H CH₃ C₃F₇ F H C₂H₅ C₃F₇ F H n-C₃H₇ C₃F₇ F H n-C₄H₉ C₃F₇ F H n-C₅H₁₁ C₃F₇ F H n-C₆H₁₃ C₃F₇ F H H C₃F₇ F F CH₃ C₃F₇ F F C₂H₅ C₃F₇ F F n-C₃H₇ C₃F₇ F F n-C₄H₉ C₃F₇ F F n-C₅H₁₁ C₃F₇ F F n-C₆H₁₃ C₃F₇ F F H SF₅ H H CH₃ SF₅ H H C₂H₅ SF₅ H H n-C₃H₇ SF₅ H H n-C₄H₉ SF₅ H H n-C₅H₁₁ SF₅ H H n-C₆H₁₃ SF₅ H H H SF₅ F H CH₃ SF₅ F H C₂H₅ SF₅ F H n-C₃H₇ SF₅ F H n-C₄H₉ SF₅ F H n-C₅H₁₁ SF₅ F H n-C₆H₁₃ SF₅ F H H SF₅ F F CH₃ SF₅ F F C₂H₅ SF₅ F F n-C₃H₇ SF₅ F F n-C₄H₉ SF₅ F F n-C₅H₁₁ SF₅ F F n-C₆H₁₃ SF₅ F F H CN H H CH₃ CN H H C₂H₅ CN H H n-C₃H₇ CN H H n-C₄H₉ CN H H n-C₅H₁₁ CN H H n-C₆H₁₃ CN H H

EXAMPLE 5

Step 5.1

A mixture of 98 mmol of Q and 16.3 ml of triethylamine (117 mmol) in 80 ml of dichloromethane is added dropwise with stirring to a solution, cooled to −70° C., of 65 mmol of P in 100 ml of dichloromethane. When the addition is complete, the mixture is stirred at −70° C. for a further 1 hour. 325 mmol of triethylamine trishydrofluoride are subsequently added dropwise at the same temperature. 325 mmol of bromine are subsequently added dropwise at −70° C. After stirring at −70° C. for one hour, the reaction mixture is allowed to warm to 10° C. and is poured into a mixture of 500 ml of ice-water and 95 ml of 32% sodium hydroxide solution. The phases are separated, and the aqueous phase is extracted with dichloromethane. The combined organic phases are subjected to conventional work-up.

Step 5.2

A mixture of 10 mmol of S and 10 mmol of 2,6-difluoro-4-(trans-5′-propyltetrahydropyranyl-(2))-phenylboronic acid in 60 ml of toluene and 60 ml of sodium borate buffer solution (pH=9) is warmed at 80° C. for 16 hours with stirring with 0.5 mmol of Pd(PPh₃)₄. After cooling, the two-phase reaction mixture is poured into 100 ml of 0.1 N HCl with stirring, the organic phase is separated off, and the aqueous phase is extracted twice with toluene. The combined toluene phases are dried and evaporated, and the residue is filtered through silica gel (heptane/methyl tert-butyl ether). Finally, the product is recrystallized first from ethanol and then from n-heptane. C 115 N 197.7 l; Δε=35.4; Δn=0.1706

The following compounds of the formula

are prepared analogously:

R¹ X L¹ L² L³ L⁴ H F H H H H CH₃ F H H H H C₂H₅ F H H H H C₃H₇ F H H H H n-C₄H₉ F H H H H n-C₅H₁₁ F H H H H n-C₆H₁₃ F H H H H H F F H H H CH₃ F F H H H C₂H₅ F F H H H n-C₃H₇ F F H H H n-C₄H₉ F F H H H n-C₅H₁₁ F F H H H n-C₆H₁₃ F F H H H H F F F H H CH₃ F F F H H n-C₄H₉ F F F H H n-C₅H₁₁ F F F H H n-C₆H₁₃ F F F H H H Cl H H H H CH₃ Cl H H H H C₂H₅ Cl H H H H n-C₃H₇ Cl H H H H n-C₄H₉ Cl H H H H n-C₅H₁₁ Cl H H H H n-C₆H₁₃ Cl H H H H H Cl F H H H CH₃ Cl F H H H C₂H₅ Cl F H H H n-C₃H₇ Cl F H H H n-C₄H₉ Cl F H H H n-C₅H₁₁ Cl F H H H n-C₆H₁₃ Cl F H H H H Cl F F H H CH₃ Cl F F H H C₂H₅ Cl F F H H n-C₃H₇ Cl F F H H n-C₄H₉ Cl F F H H n-C₅H₁₁ Cl F F H H n-C₆H₁₃ Cl F F H H H OCF₃ H H H H CH₃ OCF₃ H H H H C₂H₅ OCF₃ H H H H n-C₃H₇ OCF₃ H H H H n-C₄H₉ OCF₃ H H H H n-C₅H₁₁ OCF₃ H H H H n-C₆H₁₃ OCF₃ H H H H H OCF₃ F H H H CH₃ OCF₃ F H H H C₂H₅ OCF₃ F H H H n-C₃H₇ OCF₃ F H H H n-C₄H₉ OCF₃ F H H H n-C₅H₁₁ OCF₃ F H H H n-C₆H₁₃ OCF₃ F H H H H OCF₃ F F H H CH₃ OCF₃ F F H H C₂H₅ OCF₃ F F H H n-C₃H₇ OCF₃ F F H H n-C₄H₉ OCF₃ F F H H n-C₅H₁₁ OCF₃ F F H H n-C₆H₁₃ OCF₃ F F H H H OCHF₂ H H H H CH₃ OCHF₂ H H H H C₂H₅ OCHF₂ H H H H n-C₃H₇ OCHF₂ H H H H n-C₄H₉ OCHF₂ H H H H n-C₅H₁₁ OCHF₂ H H H H n-C₆H₁₃ OCHF₂ H H H H H OCHF₂ F H H H CH₃ OCHF₂ F H H H C₂H₅ OCHF₂ F H H H n-C₃H₇ OCHF₂ F H H H n-C₄H₉ OCHF₂ F H H H n-C₅H₁₁ OCHF₂ F H H H n-C₆H₁₃ OCHF₂ F H H H H OCHF₂ F F H H CH₃ OCHF₂ F F H H C₂H₅ OCHF₂ F F H H n-C₃H₇ OCHF₂ F F H H n-C₄H₉ OCHF₂ F F H H n-C₅H₁₁ OCHF₂ F F H H n-C₆H₁₃ OCHF₂ F F H H H OCHFCF₃ H H H H CH₃ OCHFCF₃ H H H H C₂H₅ OCHFCF₃ H H H H n-C₃H₇ OCHFCF₃ H H H H n-C₄H₉ OCHFCF₃ H H H H n-C₅H₁₁ OCHFCF₃ H H H H n-C₆H₁₃ OCHFCF₃ H H H H H OCHFCF₃ F H H H CH₃ OCHFCF₃ F H H H C₂H₅ OCHFCF₃ F H H H n-C₃H₇ OCHFCF₃ F H H H n-C₄H₉ OCHFCF₃ F H H H n-C₅H₁₁ OCHFCF₃ F H H H n-C₆H₁₃ OCHFCF₃ F H H H H OCHFCF₃ F F H H CH₃ OCHFCF₃ F F H H C₂H₅ OCHFCF₃ F F H H n-C₃H₇ OCHFCF₃ F F H H n-C₄H₉ OCHFCF₃ F F H H n-C₅H₁₁ OCHFCF₃ F F H H n-C₆H₁₃ OCHFCF₃ F F H H H OCHFCF₃ H H H H CH₃ OCHFCF₃ H H H H C₂H₅ OCHFCF₃ H H H H n-C₃H₇ OCHFCF₃ H H H H n-C₄H₉ OCHFCF₃ H H H H n-C₅H₁₁ OCHFCF₃ H H H H n-C₆H₁₃ OCHFCF₃ H H H H H OCHFCF₃ F H H H CH₃ OCHFCF₃ F H H H C₂H₅ OCHFCF₃ F H H H n-C₃H₇ OCHFCF₃ F H H H n-C₄H₉ OCHFCF₃ F H H H n-C₅H₁₁ OCHFCF₃ F H H H n-C₆H₁₃ OCHFCF₃ F H H H H OCHFCF₃ F F H H CH₃ OCHFCF₃ F F H H C₂H₅ OCHFCF₃ F F H H n-C₃H₇ OCHFCF₃ F F H H n-C₄H₉ OCHFCF₃ F F H H n-C₅H₁₁ OCHFCF₃ F F H H n-C₆H₁₃ OCHFCF₃ F F H H H OCF₂CHFCF₃ H H H H CH₃ OCF₂CHFCF₃ H H H H C₂H₅ OCF₂CHFCF₃ H H H H n-C₃H₇ OCF₂CHFCF₃ H H H H n-C₄H₉ OCF₂CHFCF₃ H H H H n-C₅H₁₁ OCF₂CHFCF₃ H H H H n-C₆H₁₃ OCF₂CHFCF₃ H H H H H OCF₂CHFCF₃ F H H H CH₃ OCF₂CHFCF₃ F H H H C₂H₅ OCF₂CHFCF₃ F H H H n-C₃H₇ OCF₂CHFCF₃ F H H H n-C₄H₉ OCF₂CHFCF₃ F H H H n-C₅H₁₁ OCF₂CHFCF₃ F H H H n-C₆H₁₃ OCF₂CHFCF₃ F H H H H OCF₂CHFCF₃ F F H H CH₃ OCF₂CHFCF₃ F F H H C₂H₅ OCF₂CHFCF₃ F F H H n-C₃H₇ OCF₂CHFCF₃ F F H H n-C₄H₉ OCF₂CHFCF₃ F F H H n-C₅H₁₁ OCF₂CHFCF₃ F F H H n-C₆H₁₃ OCF₂CHFCF₃ F F H H H NCS H H H H CH₃ NCS H H H H C₂H₅ NCS H H H H n-C₃H₇ NCS H H H H n-C₄H₉ NCS H H H H n-C₅H₁₁ NCS H H H H n-C₆H₁₃ NCS H H H H H NCS F H H H CH₃ NCS F H H H C₂H₅ NCS F H H H n-C₃H₇ NCS F H H H n-C₄H₉ NCS F H H H n-C₅H₁₁ NCS F H H H n-C₆H₁₃ NCS F H H H H NCS F F H H CH₃ NCS F F H H C₂H₅ NCS F F H H n-C₃H₇ NCS F F H H n-C₄H₉ NCS F F H H n-C₅H₁₁ NCS F F H H n-C₆H₁₃ NCS F F H H H C₂F₅ H H H H CH₃ C₂F₅ H H H H C₂H₅ C₂F₅ H H H H n-C₃H₇ C₂F₅ H H H H n-C₄H₉ C₂F₅ H H H H n-C₅H₁₁ C₂F₅ H H H H n-C₆H₁₃ C₂F₅ H H H H H C₂F₅ F H H H CH₃ C₂F₅ F H H H C₂H₅ C₂F₅ F H H H n-C₃H₇ C₂F₅ F H H H n-C₄H₉ C₂F₅ F H H H n-C₅H₁₁ C₂F₅ F H H H n-C₆H₁₃ C₂F₅ F H H H H C₂F₅ F F H H CH₃ C₂F₅ F F H H C₂H₅ C₂F₅ F F H H n-C₃H₇ C₂F₅ F F H H n-C₄H₉ C₂F₅ F F H H n-C₅H₁₁ C₂F₅ F F H H n-C₆H₁₃ C₂F₅ F F H H H C₃F₇ H H H H CH₃ C₃F₇ H H H H C₂H₅ C₃F₇ H H H H n-C₃H₇ C₃F₇ H H H H n-C₄H₉ C₃F₇ H H H H n-C₅H₁₁ C₃F₇ H H H H n-C₆H₁₃ C₃F₇ H H H H H C₃F₇ F H H H CH₃ C₃F₇ F H H H C₂H₅ C₃F₇ F H H H n-C₃H₇ C₃F₇ F H H H n-C₄H₉ C₃F₇ F H H H n-C₅H₁₁ C₃F₇ F H H H n-C₆H₁₃ C₃F₇ F H H H H C₃F₇ F F H H CH₃ C₃F₇ F F H H C₂H₅ C₃F₇ F F H H n-C₃H₇ C₃F₇ F F H H n-C₄H₉ C₃F₇ F F H H n-C₅H₁₁ C₃F₇ F F H H n-C₆H₁₃ C₃F₇ F F H H H SF₅ H H H H CH₃ SF₅ H H H H C₂H₅ SF₅ H H H H n-C₃H₇ SF₅ H H H H n-C₄H₉ SF₅ H H H H n-C₅H₁₁ SF₅ H H H H n-C₆H₁₃ SF₅ H H H H H SF₅ F H H H CH₃ SF₅ F H H H C₂H₅ SF₅ F H H H n-C₃H₇ SF₅ F H H H n-C₄H₉ SF₅ F H H H n-C₅H₁₁ SF₅ F H H H n-C₆H₁₃ SF₅ F H H H H SF₅ F F H H CH₃ SF₅ F F H H C₂H₅ SF₅ F F H H n-C₃H₇ SF₅ F F H H n-C₄H₉ SF₅ F F H H n-C₅H₁₁ SF₅ F F H H n-C₆H₁₃ SF₅ F F H H H CN H H H H CH3 CN H H H H C₂H₅ CN H H H H n-C₃H₇ CN H H H H n-C₄H₉ CN H H H H n-C₅H₁₁ CN H H H H n-C₆H₁₃ CN H H H H H CN F H H H CH₃ CN F H H H C₂H₅ CN F H H H n-C₃H₇ CN F H H H n-C₄H₉ CN F H H H n-C₅H₁₁ CN F H H H n-C₆H₁₃ CN F H H H H CN F F H H CH₃ CN F F H H C₂H₅ CN F F H H n-C₃H₇ CN F F H H n-C₄H₉ CN F F H H n-C₅H₁₁ CN F F H H n-C₆H₁₃ CN F F H H H F H H F H CH₃ F H H F H C₂H₅ F H H F H C₃H₇ F H H F H n-C₄H₉ F H H F H n-C₅H₁₁ F H H F H n-C₆H₁₃ F H H F H H F F H F H CH₃ F F H F H C₂H₅ F F H F H n-C₃H₇ F F H F H n-C₄H₉ F F H F H n-C₅H₁₁ F F H F H n-C₆H₁₃ F F H F H H F F F F H CH₃ F F F F H C₂H₅ F F F F H n-C₃H₇ F F F F H C 98 N 193.0 I; Δε = 37.9; Δn = 0.1649 n-C₄H₉ F F F F H n-C₅H₁₁ F F F F H n-C₆H₁₃ F F F F H H Cl H H F H CH₃ Cl H H F H C₂H₅ Cl H H F H n-C₃H₇ Cl H H F H n-C₄H₉ Cl H H F H n-C₅H₁₁ Cl H H F H n-C₆H₁₃ Cl H H F H H Cl F H F H CH₃ Cl F H F H C₂H₅ Cl F H F H n-C₃H₇ Cl F H F H n-C₄H₉ Cl F H F H n-C₅H₁₁ Cl F H F H n-C₆H₁₃ Cl F H F H H Cl F F F H CH₃ Cl F F F H C₂H₅ Cl F F F H n-C₃H₇ Cl F F F H n-C₄H₉ Cl F F F H n-C₅H₁₁ Cl F F F H n-C₆H₁₃ Cl F F F H H OCF₃ H H F H CH₃ OCF₃ H H F H C₂H₅ OCF₃ H H F H n-C₃H₇ OCF₃ H H F H n-C₄H₉ OCF₃ H H F H n-C₅H₁₁ OCF₃ H H F H n-C₆H₁₃ OCF₃ H H F H H OCF₃ F H F H CH₃ OCF₃ F H F H C₂H₅ OCF₃ F H F H n-C₃H₇ OCF₃ F H F H n-C₄H₉ OCF₃ F H F H n-C₅H₁₁ OCF₃ F H F H n-C₆H₁₃ OCF₃ F H F H H OCF₃ F F F H CH₃ OCF₃ F F F H C₂H₅ OCF₃ F F F H n-C₃H₇ OCF₃ F F F H n-C₄H₉ OCF₃ F F F H n-C₅H₁₁ OCF₃ F F F H n-C₆H₁₃ OCF₃ F F F H H OCHF₂ H H F H CH₃ OCHF₂ H H F H C₂H₅ OCHF₂ H H F H n-C₃H₇ OCHF₂ H H F H n-C₄H₉ OCHF₂ H H F H n-C₅H₁₁ OCHF₂ H H F H n-C₆H₁₃ OCHF₂ H H F H H OCHF₂ F H F H CH₃ OCHF₂ F H F H C₂H₅ OCHF₂ F H F H n-C₃H₇ OCHF₂ F H F H n-C₄H₉ OCHF₂ F H F H n-C₅H₁₁ OCHF₂ F H F H n-C₆H₁₃ OCHF₂ F H F H H OCHF₂ F F F H CH₃ OCHF₂ F F F H C₂H₅ OCHF₂ F F F H n-C₃H₇ OCHF₂ F F F H n-C₄H₉ OCHF₂ F F F H n-C₅H₁₁ OCHF₂ F F F H n-C₆H₁₃ OCHF₂ F F F H H OCHFCF₃ H H F H CH₃ OCHFCF₃ H H F H C₂H₅ OCHFCF₃ H H F H n-C₃H₇ OCHFCF₃ H H F H n-C₄H₉ OCHFCF₃ H H F H n-C₅H₁₁ OCHFCF₃ H H F H n-C₆H₁₃ OCHFCF₃ H H F H H OCHFCF₃ F H F H CH₃ OCHFCF₃ F H F H C₂H₅ OCHFCF₃ F H F H n-C₃H₇ OCHFCF₃ F H F H n-C₄H₉ OCHFCF₃ F H F H n-C₅H₁₁ OCHFCF₃ F H F H n-C₆H₁₃ OCHFCF₃ F H F H H OCHFCF₃ F F F H CH₃ OCHFCF₃ F F F H C₂H₅ OCHFCF₃ F F F H n-C₃H₇ OCHFCF₃ F F F H n-C₄H₉ OCHFCF₃ F F F H n-C₅H₁₁ OCHFCF₃ F F F H n-C₆H₁₃ OCHFCF₃ F F F H H OCHFCF₃ H H F H CH₃ OCHFCF₃ H H F H C₂H₅ OCHFCF₃ H H F H n-C₃H₇ OCHFCF₃ H H F H n-C₄H₉ OCHFCF₃ H H F H n-C₅H₁₁ OCHFCF₃ H H F H n-C₆H₁₃ OCHFCF₃ H H F H H OCHFCF₃ F H F H CH₃ OCHFCF₃ F H F H C₂H₅ OCHFCF₃ F H F H n-C₃H₇ OCHFCF₃ F H F H n-C₄H₉ OCHFCF₃ F H F H n-C₅H₁₁ OCHFCF₃ F H F H n-C₆H₁₃ OCHFCF₃ F H F H H OCHFCF₃ F F F H CH₃ OCHFCF₃ F F F H C₂H₅ OCHFCF₃ F F F H n-C₃H₇ OCHFCF₃ F F F H n-C₄H₉ OCHFCF₃ F F F H n-C₅H₁₁ OCHFCF₃ F F F H n-C₆H₁₃ OCHFCF₃ F F F H H OCF₂CHFCF₃ H H F H CH₃ OCF₂CHFCF₃ H H F H C₂H₅ OCF₂CHFCF₃ H H F H n-C₃H₇ OCF₂CHFCF₃ H H F H n-C₄H₉ OCF₂CHFCF₃ H H F H n-C₅H₁₁ OCF₂CHFCF₃ H H F H n-C₆H₁₃ OCF₂CHFCF₃ H H F H H OCF₂CHFCF₃ F H F H CH₃ OCF₂CHFCF₃ F H F H C₂H₅ OCF₂CHFCF₃ F H F H n-C₃H₇ OCF₂CHFCF₃ F H F H n-C₄H₉ OCF₂CHFCF₃ F H F H n-C₅H₁₁ OCF₂CHFCF₃ F H F H n-C₆H₁₃ OCF₂CHFCF₃ F H F H H OCF₂CHFCF₃ F F F H CH₃ OCF₂CHFCF₃ F F F H C₂H₅ OCF₂CHFCF₃ F F F H n-C₃H₇ OCF₂CHFCF₃ F F F H n-C₄H₉ OCF₂CHFCF₃ F F F H n-C₅H₁₁ OCF₂CHFCF₃ F F F H n-C₆H₁₃ OCF₂CHFCF₃ F F F H H NCS H H F H CH₃ NCS H H F H C₂H₅ NCS H H F H n-C₃H₇ NCS H H F H n-C₄H₉ NCS H H F H n-C₅H₁₁ NCS H H F H n-C₆H₁₃ NCS H H F H H NCS F H F H CH₃ NCS F H F H C₂H₅ NCS F H F H n-C₃H₇ NCS F H F H n-C₄H₉ NCS F H F H n-C₅H₁₁ NCS F H F H n-C₆H₁₃ NCS F H F H H NCS F F F H CH₃ NCS F F F H C₂H₅ NCS F F F H n-C₃H₇ NCS F F F H n-C₄H₉ NCS F F F H n-C₅H₁₁ NCS F F F H n-C₆H₁₃ NCS F F F H H C₂F₅ H H F H CH₃ C₂F₅ H H F H C₂H₅ C₂F₅ H H F H n-C₃H₇ C₂F₅ H H F H n-C₄H₉ C₂F₅ H H F H n-C₅H₁₁ C₂F₅ H H F H n-C₆H₁₃ C₂F₅ H H F H H C₂F₅ F H F H CH₃ C₂F₅ F H F H C₂H₅ C₂F₅ F H F H n-C₃H₇ C₂F₅ F H F H n-C₄H₉ C₂F₅ F H F H n-C₅H₁₁ C₂F₅ F H F H n-C₆H₁₃ C₂F₅ F H F H H C₂F₅ F F F H CH₃ C₂F₅ F F F H C₂H₅ C₂F₅ F F F H n-C₃H₇ C₂F₅ F F F H n-C₄H₉ C₂F₅ F F F H n-C₅H₁₁ C₂F₅ F F F H n-C₆H₁₃ C₂F₅ F F F H H C₃F₇ H H F H CH₃ C₃F₇ H H F H C₂H₅ C₃F₇ H H F H n-C₃H₇ C₃F₇ H H F H n-C₄H₉ C₃F₇ H H F H n-C₅H₁₁ C₃F₇ H H F H n-C₆H₁₃ C₃F₇ H H F H H C₃F₇ F H F H CH₃ C₃F₇ F H F H C₂H₅ C₃F₇ F H F H n-C₃H₇ C₃F₇ F H F H n-C₄H₉ C₃F₇ F H F H n-C₅H₁₁ C₃F₇ F H F H n-C₆H₁₃ C₃F₇ F H F H H C₃F₇ F F F H CH₃ C₃F₇ F F F H C₂H₅ C₃F₇ F F F H n-C₃H₇ C₃F₇ F F F H n-C₄H₉ C₃F₇ F F F H n-C₅H₁₁ C₃F₇ F F F H n-C₆H₁₃ C₃H₇ F F F H H SF₅ H H F H CH₃ SF₅ H H F H C₂H₅ SF₅ H H F H n-C₃H₇ SF₅ H H F H n-C₄H₉ SF₅ H H F H n-C₅H₁₁ SF₅ H H F H n-C₆H₁₃ SF₅ H H F H H SF₅ F H F H CH₃ SF₅ F H F H C₂H₅ SF₅ F H F H n-C₃H₇ SF₅ F H F H n-C₄H₉ SF₅ F H F H n-C₅H₁₁ SF₅ F H F H n-C₆H₁₃ SF₅ F H F H H SF₅ F F F H CH₃ SF₅ F F F H C₂H₅ SF₅ F F F H n-C₃H₇ SF₅ F F F H n-C₄H₉ SF₅ F F F H n-C₅H₁₁ SF₅ F F F H n-C₆H₁₃ SF₅ F F F H H CN H H F H CH₃ CN H H F H C₂H₅ CN H H F H n-C₃H₇ CN H H F H n-C₄H₉ CN H H F H n-C₅H₁₁ CN H H F H n-C₆H₁₃ CN H H F H H CN F H F H CH₃ CN F H F H C₂H₅ CN F H F H n-C₃H₇ CN F H F H n-C₄H₉ CN F H F H n-C₅H₁₁ CN F H F H n-C₆H₁₃ CN F H F H H CN F F F H CH₃ CN F F F H C₂H₅ CN F F F H n-C₃H₇ CN F F F H n-C₄H₉ CN F F F H n-C₅H₁₁ CN F F F H n-C₆H₁₃ CN F F F H H F H H F F CH₃ F H H F F C₂H₅ F H H F F n-C₄H₉ F H H F F n-C₅H₁₁ F H H F F n-C₆H₁₃ F H H F F H F F H F F CH₃ F F H F F C₂H₅ F F H F F n-C₃H₇ F F H F F n-C₄H₉ F F H F F n-C₅H₁₁ F F H F F n-C₆H₁₃ F F H F F H F F F F F CH₃ F F F F F C₂H₅ F F F F F C₂H₅ F F F F F n-C₃H₇ F F F F F C 144 N 181.4 I; Δε = 42.1; Δn = 0.1510 n-C₄H₉ F F F F F n-C₅H₁₁ F F F F F n-C₆H₁₃ F F F F F H Cl H H F F CH₃ Cl H H F F C₂H₅ Cl H H F F n-C₃H₇ Cl H H F F n-C₄H₉ Cl H H F F n-C₅H₁₁ Cl H H F F n-C₆H₁₃ Cl H H F F H Cl F H F F CH₃ Cl F H F F C₂H₅ Cl F H F F n-C₃H₇ Cl F H F F n-C₄H₉ Cl F H F F n-C₅H₁₁ Cl F H F F n-C₆H₁₃ Cl F H F F H Cl F F F F CH₃ Cl F F F F C₂H₅ Cl F F F F n-C₃H₇ Cl F F F F n-C₄H₉ Cl F F F F n-C₅H₁₁ Cl F F F F n-C₆H₁₃ Cl F F F F H OCF₃ H H F F CH₃ OCF₃ H H F F C₂H₅ OCF₃ H H F F n-C₃H₇ OCF₃ H H F F n-C₄H₉ OCF₃ H H F F n-C₅H₁₁ OCF₃ H H F F n-C₆H₁₃ OCF₃ H H F F H OCF₃ F H F F CH₃ OCF₃ F H F F C₂H₅ OCF₃ F H F F n-C₃H₇ OCF₃ F H F F C 121 N 205.2 I; Δε = 37.7; Δn = 0.1634 n-C₄H₉ OCF₃ F H F F n-C₅H₁₁ OCF₃ F H F F n-C₆H₁₃ OCF₃ F H F F H OCF₃ F F F F CH₃ OCF₃ F F F F C₂H₅ OCF₃ F F F F n-C₃H₇ OCF₃ F F F F C 128 N 201.2 I; Δε = 43.8; Δn = 0.1411 n-C₄H₉ OCF₃ F F F F n-C₅H₁₁ OCF₃ F F F F n-C₆H₁₃ OCF₃ F F F F H OCHF₂ H H F F CH₃ OCHF₂ H H F F C₂H₅ OCHF₂ H H F F n-C₃H₇ OCHF₂ H H F F n-C₄H₉ OCHF₂ H H F F n-C₅H₁₁ OCHF₂ H H F F n-C₆H₁₃ OCHF₂ H H F F H OCHF₂ F H F F CH₃ OCHF₂ F H F F C₂H₅ OCHF₂ F H F F n-C₃H₇ OCHF₂ F H F F n-C₄H₉ OCHF₂ F H F F n-C₅H₁₁ OCHF₂ F H F F n-C₆H₁₃ OCHF₂ F H F F H OCHF₂ F F F F CH₃ OCHF₂ F F F F C₂H₅ OCHF₂ F F F F n-C₃H₇ OCHF₂ F F F F n-C₄H₉ OCHF₂ F F F F n-C₅H₁₁ OCHF₂ F F F F n-C₆H₁₃ OCHF₂ F F F F H OCHFCF₃ H H F F CH₃ OCHFCF₃ H H F F C₂H₅ OCHFCF₃ H H F F n-C₃H₇ OCHFCF₃ H H F F n-C₄H₉ OCHFCF₃ H H F F n-C₅H₁₁ OCHFCF₃ H H F F n-C₆H₁₃ OCHFCF₃ H H F F H OCHFCF₃ F H F F CH₃ OCHFCF₃ F H F F C₂H₅ OCHFCF₃ F H F F n-C₃H₇ OCHFCF₃ F H F F n-C₄H₉ OCHFCF₃ F H F F n-C₅H₁₁ OCHFCF₃ F H F F n-C₆H₁₃ OCHFCF₃ F H F F H OCHFCF₃ F F F F CH₃ OCHFCF₃ F F F F C₂H₅ OCHFCF₃ F F F F n-C₃H₇ OCHFCF₃ F F F F n-C₄H₉ OCHFCF₃ F F F F n-C₅H₁₁ OCHFCF₃ F F F F n-C₆H₁₃ OCHFCF₃ F F F F H OCHFCF₃ H H F F CH₃ OCHFCF₃ H H F F C₂H₅ OCHFCF₃ H H F F n-C₃H₇ OCHFCF₃ H H F F n-C₄H₉ OCHFCF₃ H H F F n-C₅H₁₁ OCHFCF₃ H H F F n-C₆H₁₃ OCHFCF₃ H H F F H OCHFCF₃ F H F F CH₃ OCHFCF₃ F H F F C₂H₅ OCHFCF₃ F H F F n-C₃H₇ OCHFCF₃ F H F F n-C₄H₉ OCHFCF₃ F H F F n-C₅H₁₁ OCHFCF₃ F H F F n-C₆H₁₃ OCHFCF₃ F H F F H OCHFCF₃ F F F F CH₃ OCHFCF₃ F F F F C₂H₅ OCHFCF₃ F F F F n-C₃H₇ OCHFCF₃ F F F F n-C₄H₉ OCHFCF₃ F F F F n-C₅H₁₁ OCHFCF₃ F F F F n-C₆H₁₃ OCHFCF₃ F F F F H OCF₂CHFCF₃ H H F F CH₃ OCF₂CHFCF₃ H H F F C₂H₅ OCF₂CHFCF₃ H H F F n-C₃H₇ OCF₂CHFCF₃ H H F F n-C₄H₉ OCF₂CHFCF₃ H H F F n-C₅H₁₁ OCF₂CHFCF₃ H H F F n-C₆H₁₃ OCF₂CHFCF₃ H H F F H OCF₂CHFCF₃ F H F F CH₃ OCF₂CHFCF₃ F H F F C₂H₅ OCF₂CHFCF₃ F H F F n-C₃H₇ OCF₂CHFCF₃ F H F F n-C₄H₉ OCF₂CHFCF₃ F H F F n-C₅H₁₁ OCF₂CHFCF₃ F H F F n-C₆H₁₃ OCF₂CHFCF₃ F H F F H OCF₂CHFCF₃ F F F F CH₃ OCF₂CHFCF₃ F F F F C₂H₅ OCF₂CHFCF₃ F F F F n-C₃H₇ OCF₂CHFCF₃ F F F F n-C₄H₉ OCF₂CHFCF₃ F F F F n-C₅H₁₁ OCF₂CHFCF₃ F F F F n-C₆H₁₃ OCF₂CHFCF₃ F F F F H NCS H H F F CH₃ NCS H H F F C₂H₅ NCS H H F F n-C₃H₇ NCS H H F F n-C₄H₉ NCS H H F F n-C₅H₁₁ NCS H H F F n-C₆H₁₃ NCS H H F F H NCS F H F F CH₃ NCS F H F F C₂H₅ NCS F H F F n-C₃H₇ NCS F H F F n-C₄H₉ NCS F H F F n-C₅H₁₁ NCS F H F F n-C₆H₁₃ NCS F H F F H NCS F F F F CH₃ NCS F F F F C₂H₅ NCS F F F F n-C₃H₇ NCS F F F F n-C₄H₉ NCS F F F F n-C₅H₁₁ NCS F F F F n-C₆H₁₃ NCS F F F F H C₂F₅ H H F F CH₃ C₂F₅ H H F F C₂H₅ C₂F₅ H H F F n-C₃H₇ C₂F₅ H H F F n-C₄H₉ C₂F₅ H H F F n-C₅H₁₁ C₂F₅ H H F F n-C₆H₁₃ C₂F₅ H H F F H C₂F₅ F H F F CH₃ C₂F₅ F H F F C₂H₅ C₂F₅ F H F F n-C₃H₇ C₂F₅ F H F F n-C₄H₉ C₂F₅ F H F F n-C₅H₁₁ C₂F₅ F H F F n-C₆H₁₃ C₂F₅ F H F F H C₂F₅ F F F F CH₃ C₂F₅ F F F F C₂H₅ C₂F₅ F F F F n-C₃H₇ C₂F₅ F F F F n-C₄H₉ C₂F₅ F F F F n-C₅H₁₁ C₂F₅ F F F F n-C₆H₁₃ C₂F₅ F F F F H C₃F₇ H H F F CH₃ C₃F₇ H H F F C₂H₅ C₃F₇ H H F F n-C₃H₇ C₃F₇ H H F F n-C₄H₉ C₃F₇ H H F F n-C₅H₁₁ C₃F₇ H H F F n-C₆H₁₃ C₃F₇ H H F F H C₃F₇ F H F F CH₃ C₃F₇ F H F F C₂H₅ C₃F₇ F H F F n-C₃H₇ C₃F₇ F H F F n-C₄H₉ C₃F₇ F H F F n-C₅H₁₁ C₃F₇ F H F F n-C₆H₁₃ C₃F₇ F H F F H C₃F₇ F F F F CH₃ C₃F₇ F F F F C₂H₅ C₃F₇ F F F F n-C₃H₇ C₃F₇ F F F F n-C₄H₉ C₃F₇ F F F F n-C₅H₁₁ C₃F₇ F F F F n-C₆H₁₃ C₃F₇ F F F F H SF₅ H H F F CH₃ SF₅ H H F F C₂H₅ SF₅ H H F F n-C₃H₇ SF₅ H H F F n-C₄H₉ SF₅ H H F F n-C₅H₁₁ SF₅ H H F F n-C₆H₁₃ SF₅ H H F F H SF₅ F H F F CH₃ SF₅ F H F F C₂H₅ SF₅ F H F F n-C₃H₇ SF₅ F H F F n-C₄H₉ SF₅ F H F F n-C₅H₁₁ SF₅ F H F F n-C₆H₁₃ SF₅ F H F F H SF₅ F F F F CH₃ SF₅ F F F F C₂H₅ SF₅ F F F F n-C₃H₇ SF₅ F F F F n-C₄H₉ SF₅ F F F F n-C₅H₁₁ SF₅ F F F F n-C₆H13 SF₅ F F F F H CN H H F F CH₃ CN H H F F C₂H₅ CN H H F F n-C₃H₇ CN H H F F n-C₄H9 CN H H F F n-C₅H₁₁ CN H H F F n-C₆H₁₃ CN H H F F H CN F H F F CH₃ CN F H F F C₂H₅ CN F H F F n-C₃H₇ CN F H F F n-C₄H₉ CN F H F F n-C₅H₁₁ CN F H F F n-C₆H₁₃ CN F H F F H CN F F F F CH₃ CN F F F F C₂H₅ CN F F F F n-C₃H₇ CN F F F F n-C₄H₉ CN F F F F n-C₅H₁₁ CN F F F F n-C₆H₁₃ CN F F F F H CF₃ H H F F C₂H₅ CF₃ H H F F n-C₃H₇ CF₃ H H F F n-C₄H₉ CF₃ H H F F n-C₅H₁₁ CF₃ H H F F n-C₆H₁₃ CF₃ H H F F CH₂═CH CF₃ H H F F H CF₃ F F F F C₂H₅ CF₃ F F F F n-C₃H₇ CF₃ F F F F n-C₄H₉ CF₃ F F F F n-C₅H₁₁ CF₃ F F F F n-C₆H₁₃ CF₃ F F F F CH₂═CH CF₃ F F F F H F H H F F C₂H₅ F H H F F n-C₃H₇ F H H F F n-C₄H₉ F H H F F n-C₅H₁₁ F H H F F n-C₆H₁₃ F H H F F CH₂═CH F H H F F

EXAMPLE 6

Separation of the enantiomers of

In order to separate the enantiomers, 8.7 g of T are passed through a preparative enantio-HPLC column. After the two fractions have been obtained, each is recrystallized from ethanol and its optical rotation is determined.

3.18 g enantio-HPLC: 99.68% - optical rotation: +29.0° 3.74 g enantio-HPLC: 98.25% - optical rotation: −28.0°

The following racemates are separated into the enantiomers by an analogous method:

Enantio-HPLC: 99.97% - optical rotation: +32.0°Enantio-HPLC: 99.40% - optical rotation: −32.1°

Enantio-HPLC: 100.0% - optical rotation: +4.5°Enantio-HPLC: 99.9% - optical rotation: −4.9°

Enantio-HPLC: 99.98% - optical rotation: +28.5°Enantio-HPLC: 100.00% - optical rotation: −31.4°

MIXTURE EXAMPLES Example M1

CCH-5CF₃ 3.00% Clearing point [° C.]: +80.0 CCP-1F.F.F 3.00% Δn [589 nm, 20° C.]: +0.0660 CCP-2F.F.F 8.00% Δε [kHz, 20° C.]: +10.4 CCP-3F.F.F 8.00% d · Δn [20° C., μm]: 0.50 CCP-5F.F.F 5.00% Twist [°]: 90 CCP-20CF₃.F 8.00% V₁₀ [V]: 1.31 CCP-50CF₃.F 8.00% CCOC-3-3 2.00% CCOC-4-3 2.00% CCQU-2-F 10.00% CCQU-3-F 12.00% CCQU-5-F 8.00% ACQU-3-F 15.00% CCH-301 3.00% CCH-501 5.00%

Example M2

CCH-501 7.00% Clearing point [° C.]: +88.5 CCH-5CF₃ 7.00% Δn [589 nm, 20° C.]: +0.0657 CCP-2F.F.F 4.00% Δε [kHz, 20° C.]: +9.9 CCP-3F.F.F 7.00% d · Δn [20° C., μm]: 0.50 CCP-5F.F.F 5.00% Twist [°]: 90 CCP-30CF₃.F 8.00% V₁₀ [V]: 1.45 CCP-50CF₃.F 8.00% CCOC-3-3 3.00% CCOC-3-5 2.00% CCOC-4-3 4.00% CCQU-2-F 10.00% CCQU-3-F 12.00% CCQU-5-F 8.00% ACQU-3-F 15.00%

Example M3

CCH-301 7.00% Clearing point [° C.]: +81.0 CCH-501 10.00% Δn [589 nm, 20° C.]: +0.0608 CCH-5CF₃ 2.00% Δε [kHz, 20° C.]: +8.4 CCP-2F.F.F 9.00% d · Δn [20° C., μm]: 0.50 CCP-3F.F.F 4.00% Twist [°]: 90 CCP-5F.F.F 4.00% V₁₀ [V]: 1.49 CCP-30CF₃.F 2.00% CCP-50CF₃.F 4.00% CCOC-3-3 3.00% CCOC-3-5 2.00% CCOC-4-3 4.00% ACQU-3-F 15.00% CCQU-2-F 10.00% CCQU-3-F 12.00% CCQU-5-F 8.00% CCH-35 4.00%

Example M4

CCP-1F.F.F 4.00% Clearing point [° C.]: +79.0 CCP-2F.F.F 10.00% Δn [589 nm, 20° C.]: +0.0808 CCP-3F.F.F 9.00% Δε [kHz, 20° C.]: +15.5 CCP-5F.F.F 5.00% d · Δn [20° C., μm]: 0.50 CCP-30CF₃.F 5.00% Twist [°]: 90 CCP-50CF₃.F 7.00% γ₁ [20° C., mPa · s]: 150 PUQU-2-F 5.00% V₁₀ [V]: 0.98 PUQU-3-F 5.00% CCQU-2-F 11.00% CCQU-3-F 12.00% CCQU-5-F 8.00% CCGU-3-F 4.00% ACQU-3-F 15.00%

Example M5

BCH-3F.F 10.80% Clearing point [° C.]: +89.0 BCH-5F.F 9.00% Δn [589 nm, 20° C.]: +0.0930 ECCP-30CF₃ 4.50% Δε [kHz, 20° C.]: +6.2 ECCP-50CF₃ 4.50% CBC-33F 1.80% CBC-53F 1.80% CBC-55F 1.80% PCH-6F 7.20% PCH-7F 5.40% CCP-20CF₃ 7.20% CCP-30CF₃ 10.80% CCP-40CF₃ 6.30% CCP-50CF₃ 9.90% PCH-5F 9.00% ACQU-3-F 10.00%

Example M6

CCH-35 3.00% Clearing point [° C.]: +81.0 CC-3-V1 4.00% Δn [589 nm, 20° C.]: +0.0912 CCP-1F.F.F 10.00% d · Δn [20° C., μm]: 0.50 CCP-2F.F.F 9.00% Twist [°]: 90 CCP-3F.F.F 9.00% γ₁ [20° C., mPa · s]: 129 CCP-20CF₃.F 6.00% V₁₀ [V]: 1.30 CCG-V-F 9.00% CCP-20CF₃ 8.00% CCP-30CF₃ 8.00% CCP-40CF₃ 6.00% CCP-50CF₃ 7.00% PUQU-2-F 5.00% PUQU-3-F 7.00% APUQU-2-F 4.50% CGUQU-3-F 3.50% CBC-33 1.00%

Example M7

CCP-2F.F.F 11.00% Clearing point [° C.]: +80.0 CCP-20CF₃ 7.00% Δn [589 nm, 20° C.]: +0.1034 CCP-30CF₃ 8.00% d · Δn [20° C., μm]: 0.50 CCP-40CF₃ 5.00% Twist [°]: 90 PGU-2-F 8.00% V₁₀ [V]: 1.22 PGU-3-F 7.00% CC-3-V1 10.00% CCH-35 3.00% CCP-V-1 5.00% CCP-20CF₃.F 8.00% CCP-30CF₃.F 11.00% PUQU-2-F 4.00% PUQU-3-F 6.00% ACQU-3-F 7.00%

Example M8

CCP-1F.F.F 6.00% S → N [° C.]: −40.0 CCP-2F.F.F 10.00% Clearing point [° C.]: +80.0 CCP-20CF₃ 8.00% Δn [589 nm, 20° C.]: +0.1029 CCP-30CF₃ 8.00% d · Δn [20° C., μm]: 0.50 CCP-40CF₃ 6.00% Twist [°]: 90 CCP-50CF₃ 8.00% V₁₀ [V]: 1.24 PGU-2-F 8.00% PGU-3-F 7.00% CC-3-V1 8.00% CCH-35 5.00% CCP-V-1 5.00% CCP-30CF₃.F 3.00% PUQU-2-F 4.00% PUQU-3-F 6.00% ACQU-3-F 8.00%

Example M9

CC-3-V1 5.00% S → N [° C.]: −30.0 CCP-1F.F.F 5.00% Clearing point [° C.]: +85.5 CCP-2F.F.F 8.00% Δn [589 nm, 20° C.]: +0.0931 CCP-20CF₃.F 8.00% Δε [kHz, 20° C.]: 12.1 CCP-20CF₃ 5.00% γ₁ [20° C., mPa · s]: 135 CCP-30CF₃ 8.00% d · Δn [20° C., μm]: 0.50 CCP-40CF₃ 6.00% Twist [°]: 90 CCP-50CF₃ 8.00% V₁₀ [V]: 1.23 PUQU-2-F 5.00% PUQU-3-F 7.00% PGU-2-F 5.00% CCP-V-1 10.00% ACQU-3-F 12.00% ACQU-4-F 8.00%

Example M10

CC-3-V1 6.00% S → N [° C.]: −40.0 CCP-1F.F.F 6.00% Clearing point [° C.]: +83.5 CCP-2F.F.F 7.00% Δn [589 nm, 20° C.]: +0.0917 CCP-20CF₃.F 10.00% Δε [kHz, 20° C.]: 11.7 CCP-20CF₃ 8.00% γ₁ [20° C., mPa · s]: 125 CCP-30CF₃ 8.00% d · Δn [20° C., μm]: 0.50 CCP-40CF₃ 6.00% Twist [°]: 90 CCP-50CF₃ 4.00% V₁₀ [V]: 1.25 PUQU-2-F 5.00% PUQU-3-F 8.00% PGU-2-F 4.00% CCP-V-1 10.00% ACQU-3-F 10.00% ACQU-4-F 8.00%

Example M11 (IPS)

CDU-2-F 5.00% Clearing point [° C.]: +81 PGU-2-F 2.50% Δn [589 nm, 20° C.]: +0.0850 CCZU-2-F 4.00% Δε [kHz, 20° C.]: 10.1 CCZU-3-F 11.00% γ₁ [20° C., mPa · s]: 98 CCP-V-1 15.00% CCQU-3-F 10.00% PUQU-2-F 4.00% PUQU-3-F 5.00% CC-3-V1 11.00% PCH-302 3.50% CC-5-V 11.00% ACQU-3-F 9.00% ACQU-4-F 9.00%

Example M12 (IPS)

PGU-2-F 9.00% Clearing point [° C.]: 81.0 PGU-3-F 2.00% Δn [589 nm, 20° C.]: 0.1090 CGZP-2-OT 8.00% Δε [kHz, 20° C.]: 11.0 CGZP-3-OT 10.00% γ₁ [20° C., mPa · s]: 100 CCP-20CF₃ 6.00% CCP-30CF₃ 6.50% PUQU-2-F 4.00% PUQU-3-F 3.50% CCP-V-1 9.00% CC-3-V1 11.00% PCH-302 15.00% ACQU-3-F 8.00% ACQU-4-F 8.00%

Example M13

CC-4-V 17.00% Clearing point [° C.]: 74.5 CC-3-V1 3.00% Δn [589 nm, 20° C.]: +0.0890 CCQU-2-F 12.00% Δε [kHz, 20° C.]: 12.7 CCQU-3-F 12.00% γ₁ [20° C., mPa · s]: 119 CCQU-5-F 10.00% V₁₀ [V]: 1.09 CCP-20CF₃ 5.00% PGU-2-F 3.00% PGU-3-F 6.00% AUUQGU-3-F 8.00% CCP-1F.F.F 8.00% CCP-3F.F.F 9.00% BCH-3F.F.F 7.00%

Example M14

CC-3-V1 6.00% S → N [° C.]: <−40.0 CCP-1F.F.F 9.00% Clearing point [° C.]: 83.5 CCP-2F.F.F 9.00% Δn [589 nm, 20° C.]: 0.0941 CCP-3F.F.F 10.00% Δε [kHz, 20° C.]: 11.4 CCQU-3-F 11.00% γ₁ [20° C., mPa · s]: 137 CCQU-5-F 9.00% V₁₀ [V]: 1.23 CCP-20CF₃ 6.00% CCP-30CF₃ 8.00% CCP-50CF₃ 2.00% CGU-2-F 4.00% PGU-2-F 6.00% PGU-3-F 6.00% CCP-V-1 7.00% ACQU-3-F 7.00%

Example M15

CC-3-V1 5.00% S → N [° C.]: <−40.0 CCP-1F.F.F 7.00% Clearing point [° C.]: 84.0 CCP-2F.F.F 10.00% Δn [589 nm, 20° C.]: 0.0919 ACQU-1-F 8.00% Δε [kHz, 20° C.]: 11.9 ACQU-3-F 8.00% γ₁ [20° C., mPa · s]: 135 CCG-V-F 11.00% V₁₀ [V]: 1.19 BCH-3F.F 2.50% CCP-20CF₃ 8.00% CCP-30CF₃ 8.00% CCP-40CF₃ 5.00% CCP-V-1 8.00% PUQU-2-F 5.50% PUQU-3-F 8.00% CCGU-3-F 6.00%

Example M16

CC-3-V1 5.00% CCP-1F.F.F 7.00% CCP-2F.F.F 6.00% CCQU-3-F 10.00% CCG-V-F 6.00% CCP-20CF₃ 8.00% CCP-30CF₃ 8.00% CCP-40CF₃ 6.00% CCP-50CF₃ 8.00% ACQU-2-F 6.00% ACQU-3-F 6.00% PUQU-2-F 5.00% PUQU-3-F 7.00% PGU-3-F 6.00% CCP-V-1 6.00%

Example M17

CCP-20CF₃ 8.00% S → N [° C.]: <−30.0 CCP-30CF₃ 8.00% Clearing point [° C.]: 75.0 CCP-40CF₃ 5.00% Δn [589 nm, 20° C.]: 0.0858 PGU-2-F 5.00% Δε [kHz, 20° C.]: 13.3 PGU-3-F 5.00% γ₁ [20° C., mPa · s]: 152 CCP-1F.F.F 10.00% V₁₀ [V]: 1.07 CCP-2F.F.F 11.00% CCP-3F.F.F 12.00% CCZU-2-F 3.00% CCZU-3-F 13.00% ACQU-2-F 8.00% ACQU-3-F 8.00% ACQU-5-F 4.00%

Example M18

CC-4-V 11.00% S → N [° C.]: <−40.0 CDU-2-F 7.00% Clearing point [° C.]: 76.5 CDU-3-F 8.00% Δn [589 nm, 20° C.]: 0.0870 CDU-5-F 9.00% Δε [kHz, 20° C.]: 13.6 CCP-1F.F.F 8.50% γ₁ [20° C., mPa · s]: 146 CCP-20CF₃ 8.00% V₁₀ [V]: 1.09 CCP-30CF₃ 6.50% PGU-2-F 3.00% PGU-3-F 6.00% CCGU-3-F 6.00% CBC-33 3.00% ACQU-2-F 8.00% ACQU-3-F 8.00% ACQU-5-F 8.00%

Example M19

CC-4-V 10.00% S → N [° C.]: <−40.0 CCP-1F.F.F 9.00% Clearing point [° C.]: 75.0 CCP-2F.F.F 9.00% Δn [589 nm, 20° C.]: 0.0869 CCP-30CF₃.F 8.00% Δε [kHz, 20° C.]: 13.1 CCP-20CF₃ 8.00% γ₁ [20° C., mPa · s]: 128 CCP-30CF₃ 8.00% V₁₀ [V]: 1.06 ACQU-2-F 8.00% ACQU-3-F 8.00% ACQU-4-F 8.00% PGU-2-F 2.00% PUQU-2-F 5.00% PUQU-3-F 8.00% CCGU-3-F 6.00% CBC-33 3.00%

Example M20

CC-4-V 18.00% S → N [° C.]: <−40.0 CC-3-V1 3.00% Clearing point [° C.]: 75.0 CCQU-2-F 11.00% Δn [589 nm, 20° C.]: 0.0891 CCQU-3-F 12.00% Δε [kHz, 20° C.]: 13.0 CCQU-5-F 8.00% γ₁ [20° C., mPa · s]: 113 CCP-20CF₃ 8.00% V₁₀ [V]: 1.08 PGU-2-F 2.00% PGU-3-F 6.00% APUQU-2-F 8.00% APUQU-3-F 9.00% CCP-1F.F.F 7.00% CCP-2F.F.F 7.00% CCGU-3-F 1.00%

Example M21

CC-4-V 17.00% S → N [° C.]: <−40.0 PUQU-2-F 5.00% Clearing point [° C.]: 75.5 PUQU-3-F 7.00% Δn [589 nm, 20° C.]: 0.0894 CCP-20CF₃ 6.00% Δε [kHz, 20° C.]: 14.0 CCP-30CF₃ 5.00% γ₁ [20° C., mPa · s]: 120 CCP-2F.F.F 5.00% V₁₀ [V]: 1.06 CCZU-2-F 3.00% CCZU-3-F 13.00% PGU-3-F 6.00% ACQU-1-F 8.00% ACQU-3-F 8.00% ACQU-4-F 8.00% CCGU-3-F 6.00% CBC-33 3.00%

Example M22

CC-4-V 16.00% S → N [° C.]: <−40.0 CC-3-V1 8.00% Clearing point [° C.]: 75.5 CCP-1F.F.F 5.00% Δn [589 nm, 20° C.]: 0.0916 CCP-2F.F.F 6.00% Δε [kHz, 20° C.]: 13.6 CCQU-2-F 10.00% γ₁ [20° C., mPa · s]: 107 CCQU-3-F 12.00% V₁₀ [V]: 1.08 CCP-20CF₃ 4.00% CCZU-3-F 13.00% PGU-2-F 5.00% PGU-3-F 5.00% APUQU-2-F 8.00% APUQU-3-F 8.00%

Example M23

CCP-1F.F.F 6.00% Clearing point [° C.]: 78.2 CCP-2F.F.F 9.00% Δn [589 nm, 20° C.]: 0.0791 CCP-3F.F.F 6.00% Δε [kHz, 20° C.]: 14.3 CCP-5F.F.F 4.00% CCP-20CF₃.F 5.00% CCP-30CF₃.F 5.00% CCP-50CF₃.F 7.00% CDU-2-F 7.00% CDU-3-F 10.00% CDU-5-F 10.00% CGU-3-F 4.00% CCGU-3-F 9.00% ACQU-3-F 18.00%

Example M24

CCQU-2-F 13.00% Clearing point [° C.]: 84.5 CCQU-3-F 14.00% Δn [589 nm, 20° C.]: 0.0779 CCQU-5-F 13.00% Δε [kHz, 20° C.]: 18.7 ACQU-5-F 33.00% γ₁ [20° C., mPa · s]: 182 APUQU-2-F 7.00% V₁₀ [V]: 0.95 APUQU-3-F 9.00% CC-4-V 11.00%

Example M25

CC-4-V 18.00% Clearing point [° C.]: 74.5 CC-3-V1 5.00% Δn [589 nm, 20° C.]: 0.0882 CCP-2F.F.F 8.00% Δε [kHz, 20° C.]: 12.9 CCQU-2-F 9.00% γ₁ [20° C., mPa · s]: 103 CCQU-3-F 11.00% V₁₀ [V]: 1.09 CCQU-5-F 11.00% CCQG-3-F 6.00% BCH-3F.F.F 8.00% APUQU-2-F 6.00% APUQU-3-F 6.00% PUQU-2-F 3.00% PUQU-3-F 6.00% CCGU-3-F 1.50% PGP-2-3 1.50%

Example M26 (IPS)

CCP-20CF₃ 7.00% Clearing point [° C.]: 80.0 CCP-30CF₃ 7.00% Δn [589 nm, 20° C.]: 0.1102 CCP-40CF₃ 7.00% Δε [kHz, 20° C.]: 11.1 CCP-50CF₃ 3.50% γ₁ [20° C., mPa · s]: 82 CCZU-3-F 5.00% V₁₀ [V]: 1.13 PGU-2-F 9.00% PGU-3-F 8.00% PUQU-2-F 6.00% PUQU-3-F 6.00% CC-3-V1 13.00% CC-4-V 14.00% CCP-V-1 8.00% APUQU-2-F 6.50%

Example M27 (IPS)

CCP-20CF₃ 8.00% Clearing point [° C.]: 79.5 CCP-30CF₃ 8.00% Δn [589 nm, 20° C.]: 0.1095 CCP-40CF₃ 8.00% Δε [kHz, 20° C.]: 11.4 CCZU-3-F 5.00% γ₁ [20° C., mPa · s]: 87 PGU-2-F 9.00% V₁₀ [V]: 1.11 PGU-3-F 8.50% PUQU-2-F 6.00% PUQU-3-F 5.00% CC-3-V1 12.50% CC-4-V 14.00% CCP-V-1 9.00% AGUQU-2-F 3.50% AGUQU-3-F 3.50%

Example M28 (IPS)

CCP-2F.F.F 6.50% Clearing point [° C.]: 78.0 CCP-30CF₃ 6.00% Δn [589 nm, 20° C.]: 0.0805 CCZU-2-F 4.00% Δε [kHz, 20° C.]: 14.8 CCZU-3-F 15.00% γ₁ [20° C., mPa · s]: 121 CDU-2-F 9.00% CDU-3-F 4.00% CCQU-3-F 13.00% CCQU-5-F 10.00% PUQU-2-F 5.00% PUQU-3-F 5.00% APUQU-2-F 6.00% CC-3-V1 12.00% CC-4-V 4.50%

Example 28 (IPS)

CDU-2-F 9.00% Clearing point [° C.]: 76.5 CDU-3-F 8.00% Δn [589 nm, 20° C.]: 0.0960 PGU-2-F 9.00% Δε [kHz, 20° C.]: 12.7 CCZU-2-F 4.00% γ₁ [20° C., mPa · s]: 92 CCZU-3-F 11.00% V₁₀ [V]: 1.02 PUQU-2-F 4.00% PUQU-3-F 6.00% APUQU-2-F 7.00% CCP-V-1 14.50% CC-3-V1 12.50% CC-4-V 10.00% CCH-35 5.00%

Example M30 (IPS)

CCP-30CF₃ 3.50% Clearing point [° C.]: 75.5 CDU-2-F 5.00% Δn [589 nm, 20° C.]: 0.0975 PGU-2-F 6.50% Δε [kHz, 20° C.]: 8.4 PUQU-2-F 8.00% γ₁ [20° C., mPa · s]: 67 PUQU-3-F 8.00% V₁₀ [V]: 1.28 CCP-V-1 13.00% CCP-V2-1 9.50% CC-3-V1 13.00% CC-5-V 9.00% CC-4-V 14.00% PCH-302 3.50% APUQU-2-F 7.00%

Example M31 (IPS)

PGU-2-F 6.50% Clearing point [° C.]: 74.0 CDU-2-F 9.00% Δn [589 nm, 20° C.]: 0.1005 PUQU-2-F 11.00% Δε [kHz, 20° C.]: 14.1 PUQU-3-F 10.00% γ₁ [20° C., mPa · s]: 92 CCP-30CF₃ 8.00% CCZU-3-F 11.50% CC-4-V 10.00% CC-5-V 3.00% CC-3-V1 11.00% CCP-V2-1 13.00% APUQU-2-F 7.00%

Example M32

CCQU-2-F 10.00% Clearing point [° C.]: 82.0 CCQU-3-F 12.00% Δn [589 nm, 20° C.]: 0.0792 CCQU-5-F 8.00% Δε [kHz, 20° C.]: 11.2 CCP-1F.F.F 6.00% V₁₀ [V]: 1.20 CCP-2F.F.F 5.00% CCP-3F.F.F 5.00% CC-3-V1 10.00% CC-4-V 14.00% CGU-2-F 5.00% CCGU-3-F 5.00% ACQG-3-F 5.00% ACQG-4-F 5.00% APUQU-2-F 5.00% APUQU-3-F 5.00%

Example M33

CCQU-2-F 11.00% Clearing point [° C.]: 81.5 CCQU-3-F 13.00% Δn [589 nm, 20° C.]: 0.0804 CCQU-5-F 11.00% Δε [kHz, 20° C.]: 13.6 CCP-1F.F.F 8.00% γ₁ [20° C., mPa · s]: 153 CCP-2F.F.F 10.00% V₁₀ [V]: 1.06 CCP-3F.F.F 10.00% CCP-5F.F.F 6.00% CC-3-V1 9.00% CGU-3-F 4.00% ACQG-3-F 3.00% ACQG-4-F 5.00% APUQU-2-F 5.00% APUQU-3-F 5.00%

Example M34

CCH-5CF₃ 5.00% Clearing point [° C.]: 80.5 CCP-1F.F.F 5.00% Δn [589 nm, 20° C.]: 0.0660 CCP-2F.F.F 9.00% Δε [kHz, 20° C.]: 9.7 CCP-3F.F.F 8.00% V₁₀ [V]: 1.27 CCP-5F.F.F 5.00% CCP-20CF₃.F 6.00% CCP-50CF₃.F 6.00% CCOC-3-3 2.00% CCOC-4-3 2.00% CCQU-2-F 10.00% CCQU-3-F 12.00% CCQU-5-F 8.00% CCH-501 6.00% ACQG-3-F 8.00% ACQG-4-F 8.00%

Example M35

CCP-1F.F.F 7.00% Clearing point [° C.]: 81.5 CCP-2F.F.F 8.00% Δn [589 nm, 20° C.]: 0.0658 CCP-3F.F.F 7.00% Δε [kHz, 20° C.]: 13.5 CCP-5F.F.F 4.00% V₁₀ [V]: 1.06 CCQU-2-F 11.00% CCQU-3-F 12.00% CCQU-5-F 8.00% ACQU-2-F 8.00% ACQU-3-F 9.00% ACQU-5-F 8.00% ACQG-3-F 7.00% ACQG-4-F 5.00% CCOC-3-3 3.00% CCOC-4-3 3.00%

Example M36

AUUQU-3-F 6.00% Clearing point [° C.]: 98.0 AGUQU-3-F 6.00% Δn [589 nm, 20° C.]: 0.0927 APUQU-2-F 6.00% Δε [kHz, 20° C.]: 18.9 CGU-2-F 5.00% CGU-3-F 5.00% CGU-5-F 5.00% CCZU-2-F 5.50% CCZU-3-F 10.50% CCZU-5-F 5.50% CCQU-2-F 10.00% CCQU-3-F 10.00% CCQU-5-F 10.00% CC-5-V 9.50% CCPC-33 2.00% CCPC-34 2.00% CCPC-35 2.00%

Example M37

CCQU-2-F 7.00% Clearing point [° C.]: 85.5 CCQU-3-F 8.00% Δn [589 nm, 20° C.]: 0.0783 CCQU-5-F 8.00% Δε [kHz, 20° C.]: 11.66 CCQG-3-F 6.00% γ₁ [20° C., mPa · s]: 213 ACQU-2-F 17.00% V₁₀ [V]: 0.90 ACQU-5-F 16.00% PUQU-2-F 5.00% PUQU-3-F 5.00% CCGU-3-F 5.00% CCOC-4-3 3.00% CCZU-2-F 3.00% CCZU-3-F 14.00% CCZU-5-F 3.00%

Example M38

BCH-3F.F 10.80% Clearing point [° C.]: 56.9 BCH-5F.F 9.00% Δn [589 nm, 20° C.]: 0.0834 ECCP-30CF₃ 4.50% Δε [kHz, 20° C.]: 4.1 ECCP-50CF₃ 4.50% γ₁ [20° C., mPa · s]: 65 CBC-33F 1.80% CBC-53F 1.80% CBC-55F 1.80% PCH-6F 7.20% PCH-7F 5.40% CCP-20CF₃ 7.20% CCP-30CF₃ 10.80% CCP-40CF₃ 6.30% CCP-50CF₃ 9.90% PCH-5F 9.00% AUUQPU-3-F 10.00%

Example M39

CCP-1F.F.F 3.00% Clearing point [° C.]: 79.5 CCP-2F.F.F 6.00% Δn [589 nm, 20° C.]: 0.0796 CCP-3F.F.F 7.00% Δε [kHz, 20° C.]: 10.12 CCP-5F.F.F 5.00% γ₁ [20° C., mPa · s]: 202 CCQU-2-F 11.00% V₁₀ [V]: 0.93 CCQU-3-F 12.00% CCQU-5-F 8.00% CGU-2-F 4.00% CGU-3-F 7.00% CCGU-3-F 9.00% ACQU-2-F 8.00% ACQU-3-F 10.00% ACQU-4-F 10.00%

Example M40

CCH-5CF₃ 2.00% Clearing point [° C.]: 79.5 CCP-2F.F.F 9.00% Δn [589 nm, 20° C.]: 0.0659 CCP-3F.F.F 7.00% Δε [kHz, 20° C.]: 8.22 CCP-5F.F.F 4.00% γ₁ [20° C., mPa · s]: 169 CCP-20CF₃.F 7.00% V₁₀ [V]: 1.14 CCP-50CF₃.F 6.00% CCOC-3-3 2.00% CCOC-4-3 2.00% CCQU-2-F 10.00% CCQU-3-F 12.00% CCQU-5-F 8.00% ACQU-2-F 8.00% ACQU-3-F 10.00% ACQU-4-F 8.00% CCH-501 5.00%

Example M41

CCP-1F.F.F 6.00% Clearing point [° C.]: 80.0 CCP-2F.F.F 9.00% Δn [589 nm, 20° C.]: 0.0694 CCP-3F.F.F 10.00% Δε [kHz, 20° C.]: 8.96 CCP-5F.F.F 6.00% γ₁ [20° C., mPa · s]: 175 CCP-20CF₃.F 4.00% V₁₀ [V]: 1.11 CCP-50CF₃.F 8.00% CCQU-2-F 11.00% CCQU-3-F 12.00% CCQU-5-F 8.00% ACQU-3-F 26.00%

Example M42

CCP-1F.F.F 8.00% Clearing point [° C.]: 88.0 CCP-2F.F.F 7.00% Δn [589 nm, 20° C.]: 0.0788 CCP-3F.F.F 9.00% Δε [kHz, 20° C.]: 8.51 CCP-5F.F.F 6.00% γ₁ [20° C., mPa · s]: 192 CCP-30CF₃.F 9.00% V₁₀ [V]: 1.13 CCP-50CF₃.F 9.00% CGU-2-F 5.00% CCGU-3-F 5.00% CCQU-2-F 11.00% CCQU-3-F 12.00% CCQU-5-F 8.00% ACQU-3-F 6.00% ACQU-4-F 5.00%

Example M43

CCP-1F.F.F 2.00% Clearing point [° C.]: 81.0 CCP-20CF₃ 8.00% Δn [589 nm, 20° C.]: 0.0785 CCP-30CF₃ 8.00% Δε [kHz, 20° C.]: 7.27 CCP-40CF₃ 6.00% γ₁ [20° C., mPa · s]: 108 CCP-50CF₃ 8.00% V₁₀ [V]: 1.34 CCP-20CF₃.F 12.00% ACQU-2-F 8.00% ACQU-3-F 8.00% ACQU-4-F 8.00% PUQU-2-F 5.00% PUQU-3-F 7.00% CC-3-V1 8.00% CC-4-V 9.00% CCOC-4-3 3.00%

Example M44

CC-3-V1 5.00% S → N [° C.]: <20.0 CCP-1F.F.F 8.00% Clearing point [° C.]: 82.5 CCP-2F.F.F 10.00% Δn [589 nm, 20° C.]: 0.0939 CCQU-2-F 10.00% Δε [kHz, 20° C.]: 10.6 CCQU-3-F 5.00% γ₁ [20° C., mPa · s]: 128 CCP-20CF₃ 8.00% V₁₀ [V]: 1.19 CCP-30CF₃ 8.00% CGU-2-F 9.00% PGU-3-F 5.00% CCP-V-1 6.00% CCG-V-F 18.00% APUQU-3-F 8.00%

Example M45

CCP-2F.F.F 7.00% Clearing point [° C.]: 88.0 CCP-3F.F.F 6.00% Δn [589 nm, 20° C.]: 0.0720 CCP-5F.F.F 6.00% Δε [kHz, 20° C.]: 16.1 ACQU-2-F 10.00% γ₁ [20° C., mPa · s]: 210 ACQU-3-F 10.00% V₁₀ [V]: 0.97 ACQU-5-F 11.00% CCQU-2-F 10.00% CCQU-3-F 12.00% CCQU-5-F 10.00% CCGU-3-F 5.00% CCZU-2-F 4.00% CCZU-3-F 9.00% 

1. A liquid-crystalline compound of the formula I:

in which R¹ and R² each, independently of one another, denote H, halogen, a halogenated or unsubstituted alkyl or alkoxy radical having 1 to 15 C atoms, where one or more CH₂ groups in these radicals, independently of one another, are optionally replaced by —C≡C—, —CH═CH—, —O—, —CO—O— or —O—CO— in such a way that O atoms are not linked directly to one another, and where one of the radicals R¹ and R² is optionally CN, OCN, SCN, NCS or SF₅, A¹, A², A³ and A⁴ each, independently of one another, denote

Z¹, Z² and Z³ each, independently of one another, denote —CO—O—, —O—CO—, —CF₂O—, —OCF₂—, —CH₂O—, —OCH₂—, —CH₂CH₂—, —(CH₂)₄—, —C₂F₄—, —CH₂CF₂—, —CF₂CH₂—, —CF═CF—, —CH═CH—, —C≡C— or a single bond, and a, b and c each, independently of one another, denote 0, 1, 2 or 3, where a+b+c≦3.
 2. A liquid-crystalline compound of claim 1, which is of the formula IA:

in which R¹, R², a, and b have the meanings indicated in claim 1, where a+b=1 or 2, and L¹ and L² each, independently of one another, denote H or F.
 3. A liquid-crystalline compound according to formula I of claim 1, wherein a=1 and b=0 or a=0 and b=1.
 4. A liquid-crystalline compound according to claim 2, wherein L¹ denotes fluorine and L² denotes fluorine or hydrogen.
 5. A liquid-crystalline compound according to claim 2, wherein L¹ and L² denote fluorine.
 6. A liquid-crystalline compound of claim 1, which is of one of the formulae I1 to I31:

in which R¹ has the meaning indicated in claim 1 and X has the meaning of R² in claim
 1. 7. Liquid-crystalline medium comprising at least two mesogenic compounds, which comprises at least one compound of the formula I according to claim
 1. 8. Liquid-crystalline medium according to claim 7, which comprises one or more compounds selected from the group consisting of the compounds of formulae II to IX:

in which R⁰ denotes n-alkyl, oxaalkyl, fluoroalkyl, alkenyloxy or alkenyl, each having up to 9 C atoms, X⁰ denotes F, Cl, halogenated alkyl, halogenated alkenyl, halogenated alkenyloxy or halogenated alkoxy having up to 7 C atoms, Z⁰ denotes —CH═CH—, —C₂H₄—, —(CH₂)₄—, —C₂F₄—, —CH₂O—, —OCH₂—, —CF═CF—, —CF₂O—, —OCF₂— or —COO—, Y¹, Y², Y³ and Y⁴ each, independently of one another, denote H or F, and r is 0 or
 1. 9. Electro-optical liquid-crystal display containing a liquid-crystalline medium according to claim
 7. 10. A liquid-crystalline compound according to formula IA of claim 2, wherein a=1 and b=0 or a=0 and b=1.
 11. Electro-optical liquid-crystal display containing a liquid-crystalline medium according to claim
 8. 12. A liquid-crystalline compound of claim 1, which in formula I, a=0. 